Halogen-containing perylenetetracarboxylic acid derivatives and the use thereof

ABSTRACT

The invention relates to compounds of the formula (I) 
     
       
         
         
             
             
         
       
     
     in which Y 1  and Y 2  are each O or, respectively, NR a  or NR b , where R a  and R b  are each H or organyl; Z 1  to Z 4  are each O or S; R 11  to R 14 , R 21  to R 24  are each Cl, F; where 1 or 2 of the R 11  to R 14 , R 21  to R 24  radicals may also be CN and/or 1 R 11  to R 14 , R 21  to R 24  radical may be H; and where, when Y 1  is NR a , Z 1  or Z 2  may also be NR c , where R a  and R c  together are a bridging X group having from 2 to 5 atoms; and where, when Y 2  is NR b , Z 3  or Z 4  may also be NR d , where R b  and R d  together are a bridging X group having from 2 to 5 atoms;
 
to a process for preparation thereof, and to their use as emitter materials, charge transport materials or exciton transport materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/734,460, filed on Jan. 4, 2013, the entire content thereofincorporated herein by reference, which is a divisional of U.S.application Ser. No. 12/673,908, filed on Feb. 17, 2010, which is a 371of PCT/EP08/060,633, filed on Aug. 13, 2008, and claims priority toEuropean Patent Application No. 07114556.9, filed on Aug. 17, 2007.

The present invention relates to highly halogenated, especiallychlorinated and/or fluorinated, especially perhalogenated,perylenetetracarboxylic acid derivatives and to their use as emittermaterials, charge transport materials or exciton transport materials.

It is expected that, in the future, not only the classical inorganicsemiconductors but increasingly also organic semiconductors based on lowmolecular weight or polymeric materials will be used in many sectors ofthe electronics industry. In many cases, these organic semiconductorshave advantages over the classical inorganic semiconductors, for examplebetter substrate compatibility and better processability of thesemiconductor components based on them. They allow processing onflexible substrates and enable their interface orbital energies to beadjusted precisely to the particular application sector by the methodsof molecular modeling. The significantly reduced costs of suchcomponents have brought a renaissance to the field of research oforganic electronics. “Organic electronics” is concerned principally withthe development of new materials and manufacturing processes for theproduction of electronic components based on organic semiconductorlayers. These include in particular organic field-effect transistors(OFETs) and organic light-emitting diodes (OLEDs), and photovoltaics.Great potential for development is ascribed to organic field-effecttransistors, for example in memory elements and integratedoptoelectronic devices. Organic light-emitting diodes (OLEDs) exploitthe property of materials of emitting light when they are excited byelectrical current. OLEDs are particularly of interest as alternativesto cathode ray tubes and liquid-crystal displays for producing flatvisual display units. Owing to the very compact design and theintrinsically lower power consumption, devices which comprise OLEDs aresuitable especially for mobile applications, for example forapplications in cellphones, laptops, etc. Great potential fordevelopment is also ascribed to materials which have maximum transportwidths and high mobilities for light-induced excited states (highexciton diffusion lengths) and which are thus advantageously suitablefor use as an active material in so-called excitonic solar cells. It isgenerally possible with solar cells based on such materials to achievevery good quantum yields.

There is therefore a great need for organic compounds which are suitableas emitter materials, charge transport materials or exciton transportmaterials.

PCT/EP 2007/051532 (WO 2007/093643), unpublished at the priority date ofthis application, describes the use of compounds of the general formula(B)

wheren is 2, 3 or 4,at least one of the R^(n1), R^(n2), R^(n3) and R^(n4) radicals isfluorine,optionally at least one further R^(n1), R^(n2), R^(n3) and R^(n4)radical is a substituent which is selected independently from Cl and Br,and the remaining radicals are each hydrogen,Y¹ is O or NR^(a) where R^(a) is hydrogen or an organyl radical,Y² is O or NR^(b) where R^(b) is hydrogen or an organyl radical,Z¹, Z², Z³ and Z⁴ are each O,where, in the case that Y¹ is NR^(a), one of the Z¹ and Z² radicals mayalso be NR^(c), where the R^(a) and R^(c) radicals together are abridging group having from 2 to 5 atoms between the flanking bonds, andwhere, in the case that Y² is NR^(b), one of the Z³ and Z⁴ radicals mayalso be NR^(d), where the R^(b) and R^(d) radicals together are abridging group having from 2 to 5 atoms between the flanking bonds,as semiconductors, especially n-semiconductors, in organic electronics,especially for organic field-effect transistors, solar cells and organiclight-emitting diodes. H. J. Schugar (Acta Cryst. (1990), C46, 637-640)describes N,N′-dimethyloctachloroperylene-3,4:9,10-tetracarboximide, thepotential use of this compound in solar cells and the preparation ofthis compound by chlorinatingN,N′-dimethylperylene-3,4:9,10-tetracarboximide.

It has now been found that, surprisingly, highly halogenatedperylenetetracarboxylic acid derivatives of the formula (I) describedbelow are particularly advantageously suitable as emitter materials,charge transport materials or exciton transport materials. They arenotable especially as air-stable n-semiconductors with exceptionallyhigh charge mobilities. Moreover, they have advantageous properties foruse in excitonic solar cells.

The present invention therefore relates firstly to compounds of thegeneral formula (I)

in whichY¹ is O or NR^(a) where R^(a) is hydrogen or an organyl radical,Y² is O or NR^(b) where R^(b) is hydrogen or an organyl radical,Z¹, Z², Z³ and Z⁴ are each O or S andthe R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are each chlorineand/or fluorine,where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicalsmay also be CN and/or 1 R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radical may be hydrogen, andwhere, in the case that Y¹ is NR^(a), one of the Z¹ and Z² radicals mayalso be NR^(c), where the R^(a) and R^(c) radicals together are abridging X group having from 2 to 5 atoms between the flanking bonds,andwhere, in the case that Y² is NR^(b), one of the Z³ and Z⁴ radicals mayalso be NR^(d), where the R^(b) and R^(d) radicals together are abridging X group having from 2 to 5 atoms between the flanking bonds.

Excluded from the aforementioned compounds of the general formula (I)are the aforementioned octachloro-N,N′-dimethylperylimide and theheptachloro-N,N′-dimethylchloroperylimides obtainable as by-products inits preparation. The restrictions made above also apply with regard tothe use and preparation of the compounds of the formula (I) where thisis anticipated by the aforementioned documents.

The invention therefore further relates to the use of the compounds ofthe formula (I) as emitter materials, charge transport materials orexciton transport materials.

In the context of the present invention, the expression “alkyl”comprises straight-chain or branched alkyl. It is preferablystraight-chain or branched C₁-C₃₀-alkyl, especially C₁-C₂₀-alkyl andmost preferably C₁-C₁₂-alkyl. Examples of alkyl groups are especiallymethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyland n-eicosyl.

The expression alkyl also comprises alkyl radicals whose carbon chainsmay be interrupted by one or more nonadjacent groups which are selectedfrom —O—, —S—, —NR^(f)—, —C(═O)—, —S(═O)— and/or —S(═O)₂—. R^(f) ispreferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl orhetaryl. The expression alkyl also comprises substituted alkyl radicals.Substituted alkyl groups may, depending on the length of the alkylchain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5)substituents. These are preferably each independently selected fromcycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxyl,mercapto, COOH, carboxylate, SO₃H, sulfonate, NE¹E², nitro and cyano,where E¹ and E² are each independently hydrogen, alkyl, cycloalkyl,heterocycloalkyl, aryl or hetaryl. Halogen substituents are preferablyfluorine, chlorine or bromine.

Carboxylate and sulfonate are, respectively, a derivative of acarboxylic acid function or a sulfonic acid function, especially a metalcarboxylate or sulfonate, a carboxylic ester or sulfonic ester functionor a carboxamide or sulfonamide function. Cycloalkyl, heterocycloalkyl,aryl and hetaryl substituents of the alkyl groups may in turn beunsubstituted or substituted; suitable substituents are those specifiedbelow for these groups.

The above remarks regarding alkyl also apply to the alkyl moieties inalkoxy, alkylamino, alkylthio, alkylsulfynyl, alkylsulfonyl, etc.

Aryl-substituted alkyl radicals (“arylalkyl”) have at least oneunsubstituted or substituted aryl group as defined below. The alkylgroup in “arylalkyl” may bear at least one further substituent and/or beinterrupted by one or more nonadjacent groups which are selected from—O—, —S—, —NR^(f)—, —CO— and/or —SO₂—. R^(f) is as defined above.Arylalkyl is preferably phenyl-C₁-C₁₀-alkyl, more preferablyphenyl-C₁-C₄-alkyl, for example benzyl, 1-phenethyl, 2-phenethyl,1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl,2-phenbut-1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl,2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl, 1-(phenmeth)eth-1-yl,1-(phenmethyl)-1-(methyl)eth-1-yl or (phenmethyl)-1-(methyl)prop-1-yl;preferably benzyl and 2-phenethyl.

In the context of the present invention, the expression “alkenyl”comprises straight-chain and branched alkenyl groups which, depending onthe chain length, may bear one or more double bonds (e.g. 1, 2, 3, 4 ormore than 4). Preference is given to C₂-C₁₈-, particular preference toC₂-C₁₂-alkenyl groups. Straight-chain or branched alkenyl groups havingtwo double bonds are also referred to hereinafter as alkadienyl. Theexpression “alkenyl” also comprises substituted alkenyl groups which maybear one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents.Suitable substituents are, for example, selected from cycloalkyl,heterocycloalkyl, aryl, hetaryl, halogen, hydroxyl, mercapto, COOH,carboxylate, SO₃H, sulfonate, NE³E⁴, nitro and cyano, where E³ and E⁴are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl,aryl or hetaryl.

Alkenyl is then, for example, ethenyl, 1-propenyl, 2-propenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,penta-1,3-dien-1-yl, hexa-1,4-dien-1-yl, hexa-1,4-dien-3-yl,hexa-1,4-dien-6-yl, hexa-1,5-dien-1-yl, hexa-1,5-dien-3-yl,hexa-1,5-dien-4-yl, hepta-1,4-dien-1-yl, hepta-1,4-dien-3-yl,hepta-1,4-dien-6-yl, hepta-1,4-dien-7-yl, hepta-1,5-dien-1-yl,hepta-1,5-dien-3-yl, hepta-1,5-dien-4-yl, hepta-1,5-dien-7-yl,hepta-1,6-dien-1-yl, hepta-1,6-dien-3-yl, hepta-1,6-dien-4-yl,hepta-1,6-dien-5-yl, hepta-1,6-dien-2-yl, octa-1,4-dien-1-yl,octa-1,4-dien-2-yl, octa-1,4-dien-3-yl, octa-1,4-dien-6-yl,octa-1,4-dien-7-yl, octa-1,5-dien-1-yl, octa-1,5-dien-3-yl,octa-1,5-dien-4-yl, octa-1,5-dien-7-yl, octa-1,6-dien-1-yl,octa-1,6-dien-3-yl, octa-1,6-dien-4-yl, octa-1,6-dien-5-yl,octa-1,6-dien-2-yl, deca-1,4-dienyl, deca-1,5-dienyl, deca-1,6-dienyl,deca-1,7-dienyl, deca-1,8-dienyl, deca-2,5-dienyl, deca-2,6-dienyl,deca-2,7-dienyl, deca-2,8-dienyl and the like. The remarks regardingalkenyl also apply to the alkenyl groups in alkenyloxy, alkenylthio,etc.

The expression “alkynyl” comprises unsubstituted or substituted alkynylgroups which have one or more nonadjacent triple bonds, such as ethynyl,1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl,2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl,4-hexynyl, 5-hexynyl, and the like. The remarks regarding alkynyl alsoapply to the alkynyl groups in alkynyloxy, alkynylthio, etc. Substitutedalkynyls preferably bear one or more (e.g. 1, 2, 3, 4, 5 or more than 5)of the substituents specified above for alkyl.

In the context of the present invention, the expression “cycloalkyl”comprises unsubstituted or else substituted cycloalkyl groups,preferably C₃-C₈-cycloalkyl groups such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, especiallyC₅-C₈-cycloalkyl. Substituted cycloalkyl groups may have one or more(e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferablyeach independently selected from alkyl and the substituents specifiedabove for the alkyl groups. In the case of substitution, the cycloalkylgroups preferably bear one or more, for example one, two, three, four orfive, C₁-C₆-alkyl groups.

Examples of preferred cycloalkyl groups are cyclopentyl, 2- and3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-,3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-,3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4-and 5-propylcyclooctyl.

The expression cycloalkenyl comprises unsubstituted and substitutedmonounsaturated hydrocarbon groups having from 3 to 8, preferably from 5to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl,cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like. Suitablesubstituents are those specified above for cycloalkyl.

The expression bicycloalkyl preferably comprises bicyclic hydrocarbonradicals having from 5 to 10 carbon atoms, such asbicyclo[2.2.1]hept-1-yl, bicyclo[2.2.1]hept-2-yl,bicyclo[2.2.1]hept-7-yl, bicyclo[2.2.2]oct-1-yl, bicyclo[2.2.2]oct-2-yl,bicyclo[3.3.0]octyl, bicyclo[4.4.0]decyl and the like.

In the context of the present invention, the expression “aryl” comprisesmono- or polycyclic aromatic hydrocarbon radicals which may beunsubstituted or substituted. Aryl is preferably unsubstituted orsubstituted phenyl, naphthyl, indenyl, fluorenyl, anthracenyl,phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and morepreferably phenyl or naphthyl. Substituted aryls may, depending on thenumber and size of their ring systems, have one or more (e.g. 1, 2, 3,4, 5 or more than 5) substituents. They are preferably eachindependently selected from alkyl, alkoxy, cycloalkyl, heterocycloalkyl,aryl, hetaryl, halogen, hydroxyl, mercapto, COOH, carboxylate, SO₃H,sulfonate, NE⁵E⁶, nitro and cyano, where E⁵ and E⁶ are eachindependently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl orhetaryl. Halogen substituents are preferably fluorine, chlorine orbromine. Aryl is more preferably phenyl which, in the case ofsubstitution, may bear generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3substituents. These are preferably each independently selected fromalkyl and the substituents mentioned above for the alkyl groups.

Aryl which bears one or more radicals is, for example, 2-, 3- and4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethyl-phenyl, 2,4-, 2,5-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propyl-phenyl,2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3-and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-,3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl,2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-,3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3-and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-cyanophenyl.

In the context of the present invention, the expression“heterocycloalkyl” comprises nonaromatic, unsaturated or fullysaturated, cycloaliphatic groups having generally from 5 to 8 ringatoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ringcarbon atoms are replaced by heteroatoms selected from oxygen, nitrogen,sulfur and an —NR^(f)— group and which is unsubstituted or substitutedby one or more, for example 1, 2, 3, 4, 5 or 6 C₁-C₆-alkyl groups. R^(f)is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl orhetaryl. Examples of such heterocycloaliphatic groups includepyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl,imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl,thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl,tetrahydrothiophenyl, dihydrothien-2-yl, tetrahydrofuranyl,dihydrofuran-2-yl, tetrahydropyranyl, 1,2-oxazolin-5-yl,1,3-oxazolin-2-yl and dioxanyl.

In the context of the present invention, the expression “heteroaryl”comprises unsubstituted or substituted, heteroaromatic, mono- orpolycyclic groups, preferably the pyridyl, quinolinyl, acridinyl,pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl,indolyl, purinyl, indazolyl, benzotriazolyl, 1,2,3-triazolyl,1,3,4-triazolyl and carbazolyl groups, where these heterocycloaromaticgroups, in the case of substitution, may bear generally 1, 2 or 3substituents. The substituents are preferably selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, hydroxyl, carboxyl, halogen and cyano.

Nitrogen-containing 5-7-membered heterocycloalkyl or heteroaryl radicalswhich optionally comprise further heteroatoms selected from oxygen andsulfur comprise, for example, pyrrolyl, pyrazolyl, imidazolyl,triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl,imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl,triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl,isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl.

Halogen is fluorine, chlorine, bromine or iodine.

Specific examples of the R^(a) and R^(b) radicals specified in thefollowing formulae are as follows:

methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyland n-eicosyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl,2-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl,3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl,3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl,3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl,4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl,3,6,9-trioxadodecyl, 3,6,9,12-tetraoxamidecyl and3,6,9,12-tetraoxatetradecyl;2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-butylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl,3-propylthiopropyl, 3-butylthiopropyl, 4-methylthiobutyl,4-ethylthiobutyl, 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-di-thianonyl, 2- and4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl,3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiamidecyland 3,6,9,12-tetrathiatetradecyl;2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazamidecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazamidecyl;(1-ethylethylidene)aminoethylene, (1-ethylethylidene)aminopropylene,(1-ethylethylidene)aminobutylene, (1-ethylethylidene)aminodecylene and(1-ethylethylidene)aminododecylene;propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-propylsulfinylethyl,2-isopropylsulfinylethyl, 2-butylsulfinylethyl, 2- and3-methylsulfinylpropyl, 2- and 3-ethylsulfinylpropyl, 2- and3-propylsulfinylpropyl, 2- and 3-butylsulfinylpropyl, 2- and4-methylsulfinylbutyl, 2- and 4-ethylsulfinylbutyl, 2- and4-propylsulfinylbutyl and 4-butylsulfinylbutyl;2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl,2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl,12-carboxydodecyl and 14-carboxytetradecyl;sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl,6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and14-sulfotetradecyl;2-hydroxyethyl, 2- and 3-hydroxypropyl, 3- and 4-hydroxybutyl and8-hydroxy-4-oxaoctyl;2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl;2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl,2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl;2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl;methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy;methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio;ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and4-pentynyl, 1-, 2-, 3-, 4- and 5-hexynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecynyland 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-,16- and 17-octadecynyl;ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecenyland 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-,16- and 17-octadecenyl;methylamino, ethylamino, propylamino, butylamino, pentylamino,hexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino,diphenylamino and dibenzylamino;formylamino, acetylamino, propionylamino and benzoylamino;carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl,heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl,decylaminocarbonyl and phenylaminocarbonyl;aminosulfonyl, N-dodecylaminosulfonyl, N,N-diphenylaminosulfonyl, and,N-bis(4-chlorophenyl)aminosulfonyl;methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl hexoxycarbonyl,dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl,(4-tert-butyl-phenoxy)carbonyl and (4-chlorophenoxy)carbonyl;methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxysulfonyl,hexoxysulfonyl, dodecyloxysulfonyl, octadecyloxysulfonyl,phenoxysulfonyl, 1- and 2-naphthyloxysulfonyl,(4-tert-butylphenoxy)sulfonyl and (4-chlorophenoxy)sulfonyl;diphenylphosphino, di-(o-tolyl)phosphino and diphenylphosphinoxido;fluorine, chlorine, bromine and iodine;phenylazo, 2-napthylazo, 2-pyridylazo and 2-pyrimidylazo;cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3-and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-,3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl,2-, 3-, 4- and 5-ethylcyclooctyl and 3-, 4- and 5-propylcyclooctyl; 3-and 4-hydroxycyclohexyl, 3- and 4-nitrocyclohexyl and 3- and4-chlorocyclohexyl;1-, 2- and 3-cyclopentenyl, 1-, 2-, 3- and 4-cyclohexenyl, 1-, 2- and3-cycloheptenyl and 1-, 2-, 3- and 4-cyclooctenyl;2-dioxanyl, 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl,1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3-and 4-piperidyl;phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5-imidazolyl, 2-, 4- and5-thiazolyl, 3-(1,2,4-triazyl), 2-(1,3,5-triazyl), 6-quinaldyl, 3-, 5-,6- and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl,5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;1-, 2-, 3-, 4-, 5-, 6- and 7-indolyl, 1-, 2-, 3-, 4-, 5-, 6- and7-isoindolyl, 5-(4-methylisoindolyl), 5-(4-phenylisoindolyl), 1-, 2-,4-, 6-, 7- and 8-(1,2,3,4-tetrahydroisoquinolinyl),3-(5-phenyl)-(1,2,3,4-tetrahydroisoquinolinyl),5-(3-dodecyl)-(1,2,3,4-tetrahydroisoquinolinyl), 1-, 2-, 3-, 4-, 5-, 6-,7- and 8-(1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, 4-, 5-, 6-, 7- and8-chromanyl, 2-, 4- and 7-quinolinyl, 2-(4-phenylquinolinyl) and2-(5-ethylquinolinyl);2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl,2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and4-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and2,4,6-tri-sec.butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl,2,4-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxy-phenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl;3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3-and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl; 3- and4-N-phenylaminophenyl, 3- and 4-N-(o-tolyl)aminophenyl, 3- and4-N-(m-tolyl)aminophenyl and 3- and 4-(p-tolyl)aminophenyl; 3- and4-(2-pyridyl)aminophenyl, 3- and 4-(3-pyridyl)aminophenyl, 3- and4-(4-pyridyl)aminophenyl, 3- and 4-(2-pyrimidyl)aminophenyl and4-(4-pyrimidyl)aminophenyl;4-phenylazophenyl, 4-(1-naphthylazo)phenyl, 4-(2-naphthylazo)phenyl,4-(4-naphthyl-azo)phenyl, 4-(2-pyriylazo)phenyl, 4-(3-pyridylazo)phenyl,4-(4-pyridylazo)phenyl, 4-(2-pyrimidylazo)phenyl,4-(4-pyrimidylazo)phenyl and 4-(5-pyrimidylazo)phenyl;phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and2-, 4- and 5-pyrimidylthio.

Preferred fluorinated R^(a) and R^(b) radicals are as follows:

2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluoroethyl,2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,3-pentafluoropropyl,1H,1H-pentadecafluorooctyl, 3-bromo-3,3-difluoropropyl,3,3,3-trifluoropropyl, 3,3,3-trifluoropropyl,1H,1H,2H,2H-perfluorodecyl, 3-(perfluorooctyl)propyl,4,4-difluorobutyl-, 4,4,4-trifluorobutyl, 5,5,6,6,6-pentafluorohexyl,2,2-difluoropropyl, 2,2,2-trifluoro-1-phenylethylamino,1-benzyl-2,2,2-trifluoroethyl, 2-bromo-2,2-difluoroethyl,2,2,2-trifluoro-1-pyridin-2-ylethyl, 2,2-difluoropropyl,2,2,2-trifluoro-1-(4-methoxyphenyl)ethylamino,2,2,2-trifluoro-1-phenylethyl, 2,2-difluoro-1-phenylethyl,1-(4-bromo-phenyl)-2,2,2-trifluoroethyl, 3-bromo-3,3-difluoropropyl,3,3,3-trifluoropropylamine, 3,3,3-trifluoro-n-propyl,1H,1H,2H,2H-perfluorodecyl, 3-(perfluorooctyl)propyl, pentafluorophenyl,2,3,5,6-tetrafluorophenyl, 4-cyano-(2,3,5,6)-tetrafluorophenyl,4-carboxy-2,3,5,6-tetrafluorophenyl, 2,4-difluorophenyl,2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 2,5-difluorophenyl,2-fluoro-5-nitrophenyl, 2-fluoro-5-trifluoromethylphenyl,2-fluoro-5-methylphenyl, 2,6-difluorophenyl,4-carboxamido-2,3,5,6-tetrafluorophenyl, 2-bromo-4,6-difluorophenyl,4-bromo-2-fluorophenyl, 2,3-difluorophenyl, 4-chloro-2-fluorophenyl,2,3,4-trifluorophenyl, 2-fluoro-4-iodphenyl,4-bromo-2,3,5,6-tetrafluorophenyl, 2,3,6-trifluorophenyl,2-bromo-3,4,6-trifluorophenyl, 2-bromo-4,5,6-trifluorophenyl,4-bromo-2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl,2,4-difluoro-6-nitrophenyl, 2-fluoro-4-nitrophenyl,2-chloro-6-fluorophenyl, 2-fluoro-4-methylphenyl,3-chloro-2,4-difluorophenyl, 2,4-dibromo-6-fluorophenyl,3,5-dichloro-2,4-difluorophenyl, 4-cyano-2-fluorophenyl,2-chloro-4-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl,2-trifluoromethyl-6-fluorophenyl, 2,3,4,6-tetrafluorophenyl,3-chloro-2-fluorophenyl, 5-chloro-2-fluorophenyl,2-bromo-4-chloro-6-fluorophenyl, 2,3-dicyano-4,5,6-trifluorophenyl,2,4,5-trifluoro-3-carboxyphenyl, 2,3,4-trifluoro-6-carboxyphenyl,2,3,5-trifluorophenyl, 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl,2-fluoro-5-carboxyphenyl, 2-chloro-4,6-difluorophenyl,6-bromo-3-chloro-2,4-difluorophenyl, 2,3,4-trifluoro-6-nitrophenyl,2,5-difluoro-4-cyanophenyl, 2,5-difluoro-4-trifluoromethylphenyl,2,3-difluoro-6-nitrophenyl, 4-trifluoromethyl-2,3-difluorophenyl,2-bromo-4,6-difluorophenyl, 4-bromo-2-fluorophenyl,2-nitrotetrafluorophenyl, 2,2′,3,3′,4′,5,5′,6,6′-nonafluorobiphenyl,2-nitro-3,5,6-trifluorophenyl, 2-bromo-6-fluorophenyl,4-chloro-2-fluoro-6-iodphenyl, 2-fluoro-6-carboxyphenyl,2,4-difluoro-3-trifluorophenyl, 2-fluoro-4-trifluorophenyl,2-fluoro-4-carboxyphenyl, 4-bromo-2,5-difluorophenyl,2,5-dibromo-3,4,6-trifluorophenyl, 2-fluoro-5-methylsulfonylphenyl,5-bromo-2-fluorophenyl, 2-fluoro-4-hydroxymethylphenyl,3-fluoro-4-bromomethylphenyl, 2-nitro-4-trifluoromethylphenyl,4-trifluoromethylphenyl, 2-bromo-4-trifluoromethylphenyl,2-bromo-6-chloro-4-(trifluoromethyl)phenyl,2-chloro-4-trifluoromethylphenyl, 3-nitro-4-(trifluoromethyl)phenyl,2,6-dichloro-4-(trifluormethyl)phenyl, 4-trifluorophenyl,2,6-dibromo-4-(trifluoromethyl)phenyl,4-trifluoromethyl-2,3,5,6-tetrafluorophenyl,3-fluoro-4-trifluoromethylphenyl, 2,5-difluoro-4-trifluoromethylphenyl,3,5-difluoro-4-trifluoromethylphenyl,2,3-difluoro-4-trifluoromethylphenyl, 2,4-bis(trifluoromethyl)phenyl,3-chloro-4-trifluoromethylphenyl, 2-bromo-4,5-di(trifluoromethyl)phenyl,5-chloro-2-nitro-4-(trifluoromethyl)phenyl,2,4,6-tris(trifluoromethyl)phenyl, 3,4-bis(trifluoromethyl)phenyl,2-fluoro-3-trifluoromethylphenyl, 2-iod-4-trifluoromethylphenyl,2-nitro-4,5-bis(trifluoromethyl)phenyl,2-methyl-4-(trifluoromethyl)phenyl,3,5-dichloro-4-(trifluoromethyl)phenyl,2,3,6-trichloro-4-(trifluoromethyl)phenyl, 4-(trifluoromethyl)benzyl,2-fluoro-4-(trifluoromethyl)benzyl, 3-fluoro-4-(trifluoromethyl)benzyl,3-chloro-4-(trifluoromethyl)benzyl, 4-fluorophenethyl,3-(trifluoromethyl)phenethyl, 2-chloro-6-fluorophenethyl,2,6-dichlorophenethyl, 3-fluorophenethyl, 2-fluorophenethyl,(2-trifluoromethyl)phenethyl, 4-fluorophenethyl, 3-fluorophenethyl,4-trifluoromethylphenethyl, 2,3-difluorophenethyl,3,4-difluorophenethyl, 2,4-difluorophenethyl, 2,5-difluorophenethyl,3,5-difluorophenethyl, 2,6-difluorophenethyl,4-(4-fluorophenyl)phenethyl, 3,5-di(trifluoromethyl)phenethyl,pentafluorophenethyl, 2,4-di(trifluoromethyl)phenethyl,2-nitro-4-(trifluoromethyl)phenethyl,(2-fluoro-3-trifluoromethyl)phenethyl,(2-fluoro-5-trifluoromethyl)phenethyl,(3-fluoro-5-trifluoromethyl)phenethyl,(4-fluoro-2-trifluoromethyl)phenethyl,(4-fluoro-3-trifluoromethyl)phenethyl,(2-fluoro-6-trifluoromethyl)phenethyl, (2,3,6-trifluoro)phenethyl,(2,4,5-trifluoro)phenethyl, (2,4,6-trifluoro)phenethyl,(2,3,4-trifluoro)phenethyl, (3,4,5-trifluoro)phenethyl,(2,3,5-trifluoro)phenethyl, (2-chloro-5-fluoro)phenethyl,(3-fluoro-4-trifluoromethyl)phenethyl,(2-chloro-5-trifluoromethyl)phenethyl,(2-fluoro-3-chloro-5-trifluoromethyl)phenethyl,(2-fluoro-3-chloro)phenethyl, (4-fluoro-3-chloro)phenethyl,(2-fluoro-4-chloro)phenethyl, (2,3-difluoro-4-methyl)phenethyl-,2,6-difluoro-3-chlorophenethyl, (2,6-difluoro-3-methyl)phenethyl,(2-trifluoromethyl-5-chloro)phenethyl,(6-chloro-2-fluoro-5-methyl)phenethyl, (2,4-dichloro-5-fluoro)phenethyl,5-chloro-2-fluorophenethyl, (2,5-difluoro-6-chloro)phenethyl,(2,3,4,5-tetrafluoro)phenethyl, (2-fluoro-4-trifluoromethyl)phenethyl,2,3-(difluoro-4-trifluoromethyl)phenethyl,(2,5-di(trifluoromethyl))phenethyl, 2-fluoro-3,5-dibromophenethyl,(3-fluoro-4-nitro)phenethyl, (2-bromo-4-trifluoromethyl)phenethyl,2-(bromo-5-fluoro)phenethyl, (2,6-difluoro-4-bromo)phenethyl,(2,6-difluoro-4-chloro)phenethyl, (3-chloro-5-fluoro)phenethyl,(2-bromo-5-trifluoromethyl)phenethyl and the like.

A further embodiment relates to compounds of the formula (I) where theR^(a) and R^(b) groups are each groups of the formula (A) (so-calledswallowtail radicals). In the groups of the formula (A), the R^(e)radicals are preferably selected from C₄-C₈-alkyl, preferablyC₅-C₇-alkyl. The R^(a) and R^(b) groups are then each a group of theformula

in which# is the bonding site to the imide nitrogen atom andthe R^(e) radicals are selected from C₄-C₈-alkyl, preferablyC₅-C₁-alkyl. The R^(e) radicals are then especially linear alkylradicals which are not interrupted by oxygen atoms. A preferred exampleof a group of the formula (A) is 1-hexylhept-1-yl.

Preference is given to compounds of the formula (I) where the R¹¹, R¹²,R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals each have a definition otherthan hydrogen, i.e. compounds of the formula (I) where the R¹¹, R¹²,R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are each chlorine and/orfluorine, where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals may also be cyano.

Additionally preferred are compounds of the formula (I) where the R¹¹,R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are each chlorine and/orfluorine, where one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals may also be hydrogen.

Particular preference is given to compounds of the formula (I) where theR¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are all chlorineand/or fluorine. Very particular preference is given to compounds of theformula (I) where the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicalsare all chlorine or are all fluorine.

Perylenetetracarboxylic dianhydrides are referred to hereinafter ascompounds (I.A).

Perylenetetracarboximides are referred to hereinafter as compounds(I.B), where compounds (I.Ba)

do not have an additional bridging X group, and compounds (I.Bb1) and(I.Bb2)

do have such an additional bridging X group.

A first specific embodiment relates to compounds of the general formula(I.A) where R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have thedefinitions specified above.

A further specific embodiment relates to compounds of the generalformula (I.Ba) where R^(a), R^(b), R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ andR²⁴ each have one of the definitions given above.

In this specific embodiment, the R^(a) and R^(b) radicals are preferablyeach independently hydrogen or unsubstituted or substituted alkyl,alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl, cycloalkenyl,heterocycloalkyl, aryl or heteroaryl.

More preferably, at least one of the R^(a) or R^(b) radicals in thecompounds of the formula (I.Ba) is hydrogen. More preferably, both R^(a)and R^(b) are hydrogen.

In a further specific embodiment, the R^(a) and R^(b) radicals are thesame.

A further specific embodiment relates to compounds of the generalformulae (I.Bb1) and (I.Bb2) where R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ andR²⁴ each have the definitions given above and X is a divalent bridginggroup having from 2 to 5 atoms between the flanking bonds.

The bridging X groups together with the N—C═N group to which they arebonded are preferably a 5- to 8-membered heterocycle which is optionallyfused once, twice or three times to cycloalkyl, heterocycloalkyl, aryland/or hetaryl, where the fused groups may each independently bear one,two, three or four substituents selected from alkyl, alkoxy, cycloalkyl,aryl, halogen, hydroxyl, mercapto, COOH, carboxylate, SO₃H, sulfonate,NE¹E², alkylene-NE¹E², nitro and cyano, where E¹ and E² are eachindependently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl orhetaryl, and/or X may have one, two or three substituents which areselected from optionally substituted alkyl, optionally substitutedcycloalkyl and optionally substituted aryl, and/or X may be interruptedby one, two or three optionally substituted heteroatoms. The heteroatomsare preferably selected from oxygen, sulfur and nitrogen.

The bridging X groups are preferably selected from groups of theformulae (III.a) to (III.d)

in which

-   R^(IV), R^(V), R^(VI), R^(VII), R^(VIII) and R^(IX) are each    independently hydrogen, alkyl, alkoxy, cycloalkyl, cycloalkoxy,    heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl,    hetaryloxy, halogen, hydroxyl, mercapto, COOH, carboxylate, SO₃H,    sulfonate, NE¹E², alkylene-NE¹E², nitro, alkoxycarbonyl, acyl or    cyano, where E¹ and E² are each independently hydrogen, alkyl,    cycloalkyl, heterocycloalkyl, aryl or hetaryl.

In a specific embodiment, the R^(IV), R^(V), R^(VI), R^(VII), R^(VIII)and R^(IX) radicals in the (III.a) to (III.d) groups are each hydrogen.

A further specific embodiment relates to compounds of the generalformula (I), especially compounds of the formulae (I.A), (I.Ba), (I.Bb1)or (I.Bb2), in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ are eachfluorine, where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals may be CN and/or 1 R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radical may be hydrogen. However, preferably all R¹¹, R¹², R¹³, R¹⁴,R²¹, R²², R²³ and R²⁴ radicals are fluorine.

A further specific embodiment relates to compounds of the generalformula (I), especially compounds of the formulae (I.A), (I.Ba), (I.Bb1)or (I.Bb2), in which some of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ andR²⁴ radicals are fluorine and the other R¹¹, R¹², R¹³, R¹⁴, R²¹, R²²,R²³ and R²⁴ radicals are chlorine, where 1 or 2 of the R¹¹, R¹², R¹³,R¹⁴, R²¹, R²², R²³ and R²⁴ radicals may each be CN and/or 1 R¹¹, R¹²,R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radical may be hydrogen. Preferably,four of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals arefluorine and the four remaining R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ andR²⁴ radicals are chlorine.

Specific examples of suitable compounds of the formula (I) are thoseshown below:

The inventive compounds of the general formula (I) can be preparedproceeding from known compounds with the same perylene base skeletonwhich, as R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals, have atleast one hydrogen atom.

Accordingly, the present invention further relates to a process forpreparing compounds of the formula (I)

where R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴, Y¹, Y², Z¹, Z², Z³ and Z⁴each have one of the definitions given above,in which

-   a) a compound of the formula (II)

-   -   in which    -   R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ are each selected from        hydrogen, Cl and CN, and    -   Y¹, Y², Z¹, Z², Z³ and Z⁴ each have one of the definitions given        above,    -   where at least one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴        radicals is hydrogen, from 0 to 7 of the R¹¹, R¹², R¹³, R¹⁴,        R²¹, R²², R²³, R²⁴ radicals are each Cl and from 0 to 2 of the        R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ radicals are each CN,    -   is subjected to a chlorination to obtain a compound of the        formula (I)    -   in which the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals        are each chlorine, where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹,        R²², R²³ and R²⁴ radicals may also be CN, and one of the R¹¹,        R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals may be hydrogen,    -   and

-   b) optionally, the compound of the formula (I) obtained in step a)    is subjected to a partial or full exchange of chlorine for fluorine.

Step a)

Methods of chlorinating aromatics are known in principle to thoseskilled in the art. The inventive compounds of the formula (I) in whichthe R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are eachchlorine, where one of these radicals may also be hydrogen, can beprepared from the corresponding compounds of the formula (II) in whichat least one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicalsis hydrogen by reaction with a chlorinating agent such as thionylchloride, chlorosulfonic acid, sulfuryl chloride or chlorine in an inertsolvent.

A particularly preferred embodiment of the present invention relates tothe use of chlorosulfonic acid as a solvent (and not as a chlorinatingagent) in step a) of the process according to the invention. In thisconfiguration of the process, chlorine is then preferably used as thechlorinating agent.

The reaction of the compounds of the formula (II) with a chlorinatingagent takes place preferably in the presence of a catalyst. Usefulcatalysts include, for example, iodine or iodobenzene, and also mixturesthereof.

In a specific embodiment of the process, the compound of the formula(II) is chlorinated by reaction with chlorine in chlorosulfonic acid andin the presence of catalytic amounts of iodine.

The reaction temperature for the reaction with a chlorinating agent istypically within a range of from 35 to 110° C., preferably from 40 to95° C.

The reaction of the compounds of the formula (II) with a chlorinatingagent can be brought about under standard pressure or under elevatedpressure.

The compounds of the formula (I) are typically isolated from thereaction mixture by precipitation. The precipitation is brought about,for example, by adding a liquid which dissolves the compounds only to aslight degree, if at all, but is miscible with the inert solvents. Theprecipitation products can then be isolated by filtration and typicallyhave a sufficiently high purity.

For use of the products as semiconductors, it may be advantageous tosubject the product to a further purification. These include, forexample, column chromatography processes, where the products aresubjected to a separation or filtration on silca gel, for exampledissolved in a halogenated hydrocarbon such as methylene chloride or atoluene/ethyl acetate or petroleum ether/ethyl acetate mixture. Inaddition, purification by sublimation or crystallization is possible.

If required, the purification steps are repeated once or more than onceand/or different purification steps are combined in order to obtain verypure compounds (I).

In a preferred embodiment of the process according to the invention, thechlorination of the compound of the formula (II) is brought about byreaction with chlorine in chlorosulfonic acid (as a solvent) and in thepresence of catalytic amounts of iodine. In this embodiment, thecompounds of the formula (I) are preferably isolated by adding water andisolating the solid which precipitates out.

Typically, the inventive preparation of the compounds of the formula (I)will proceed from the corresponding compounds of the formula (II) inwhich all R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals arehydrogen, where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals may also be CN. In a specific embodiment, R¹¹ to R¹⁴ and R²¹ toR²⁴ are each hydrogen. However, it may also be advantageous to proceedfrom partly chlorinated compounds of the formula (II), especially whenthey are more readily obtainable owing to the increased reactivity oftheir precursor compounds.

When the R^(a), R^(b) radicals have aromatic groups, they may also bechlorinated under the chlorinating conditions described above. For thisreason, it may be appropriate first to chlorinate the perylene baseskeleton and to introduce the R^(a), R^(b) radicals thereafter, forexample by an imidation reaction.

Step b)

The preparation of the inventive compounds of the general formula (I) inwhich at least some of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals are fluorine can proceed from the compounds of the formula (I)which have the same rylene base skeleton and are provided in step a), bypartial or full exchange of chlorine for fluorine. Conditions for such ahalogen exchange are sufficiently well known to those skilled in theart. Depending on the reaction conditions selected, the halogen exchangecan be brought about fully or only partly.

In a preferred embodiment of the process according to the invention,compounds of the formula (I) in which at least some of the R¹¹, R¹²,R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are fluorine will be preparedby reacting the compound of the formula (I) obtained in step a) with analkali metal fluoride under essentially anhydrous conditions.

In the context of the invention, “essentially anhydrous conditions” areunderstood to mean a total water content, based on all componentsinvolved in the reaction (reactants, solvents, complexing agents, etc.),of at most 2% by weight, preferably of at most 1% by weight, especiallyof at most 0.1% by weight. To achieve the anhydrous reaction conditions,the components involved in the reaction can be subjected to drying bycustomary processes known to those skilled in the art.

Suitable process conditions for aromatic nucleophilic substitution ofchlorine atoms by fluorine atoms (halogen exchange) are known inprinciple. Suitable conditions for halogen exchange are described, forexample, in J. March, Advanced Organic Chemistry, 4th edition,publisher: John Wiley & Sons (1992), p. 659, and in DE 32 35 526.

In a first embodiment, the reaction is an exchange of the chlorine atomsfor fluorine atoms. To introduce the fluorine groups, preference isgiven to using an alkali metal fluoride, especially KF, NaF or CsF.Preference is given to using from 1 to 30 equivalents of alkali metalfluoride per equivalent of rylene compound.

Preferred solvents for the halogen exchange are aprotic polar solventssuch as dimethylformamide, N-methylpyrrolidone, (CH₃)₂SO, dimethylsulfone, N,N′-dimethylimidazolidinone or sulfolane. Particularpreference is given to using sulfolane as the solvent. Before use, thesolvents are preferably subjected to drying to remove water by customarymethods known to those skilled in the art. Likewise suitable are aproticsolvents such as aromatic hydrocarbons, e.g. xylenes, for exampleo-xylene.

Typically, the compound of the formula (I) obtained in step a) will besubjected to halogen exchange in the form of a solution which has aconcentration of from 0.002 to 0.2 mol/l, preferably from 0.01 to 0.1mol/l, in one of the aforementioned solvents.

For the halogen exchange, it is additionally possible to use acomplexing agent, for example a crown ether. These include, for example,[12]crown-4, [15]crown-5, [18]crown-6, [21]crown-7, [24]crown-8, etc.The complexing agent is selected according to its ability to complex thealkali metals of the alkali metal halides used for the halogen exchange.When KF is used to introduce the fluorine groups, the complexing agentused is preferably [18]crown-6. Preference is given to using from 0.1 to10 equivalents of crown ether per equivalent of rylene compound.

Further suitable phase transfer catalysts are, for example, selectedfrom 2-azaallenium compounds, carbophosphazenium compounds,aminophosphonium compounds and diphosphazenium compounds. A. Pleschke,A. Marhold, M. Schneider, A. Kolomeitsev and G. V. Röschenthaler, in theJournal of Fluorine Chemistry 125, 2004, 1031-1038, give a review ofsuitable phase transfer catalysts. Reference is made to the disclosureof this document. In a preferred embodiment, 2-azaallenium compounds,such as (N,N-dimethylimidazolidino)tetramethylguanidinium chloride, areused. The amount of these phase transfer catalysts used is preferablyfrom 0.1 to 20% by weight, preferably from 1 to 10% by weight, based onthe weight of the rylene compound used.

The reaction temperatures for the halogen exchange are preferably from100 to 200° C. The reaction time is preferably from 0.5 to 48 hours.

Compounds of the formula (II) in which 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴,R²¹, R²², R²³ and R²⁴ radicals are each CN can be brought aboutproceeding compounds with the same rylene base skeleton which have 1 or2 exchangeable chlorine atoms as R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ andR²⁴ radicals by exchange of the chlorine atoms for cyano. Conditions forsuch an exchange reaction are known to those skilled in the art.

Compounds of the formula (II) in which 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴,R²¹, R²², R²³ and R²⁴ radicals are CN may also be prepared proceedingfrom compounds with the same rylene base skeleton which possess 1 or 2exchangeable bromine atoms as R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴radicals, by exchanging the bromine atoms for cyano. Conditions for suchan exchange reaction are known to those skilled in the art.

For the exchange of bromine or chlorine for cyano, examples of suitablecompounds are alkali metal cyanides such as KCN and NaCN, and especiallyzinc cyanide. The reaction is effected preferably in the presence of atleast one transition metal catalyst. Suitable transition metal catalystsare especially palladium complexes such astetrakis(triphenylphosphine)palladium(0),tetrakis(tris-o-tolylphosphine)palladium(0),[1,2-bis(diphenylphosphino)ethane]palladium(II) chloride,[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) chloride,bis(triethylphosphine)palladium(II) chloride,bis(tricyclohexylphosphine)palladium(II) acetate,(2,2′-bipyridyl)palladium(II) chloride,bis(triphenylphosphine)palladium(II) chloride,tris(dibenzylideneacetone)dipalladium(0),1,5-cyclooctadienepalladium(II) chloride, bis(acetonitrile)palladium(II)chloride and bis(benzonitrile)palladium(II) chloride, preference beinggiven to [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) chlorideand tetrakis(triphenylphosphine)palladium(0).

For the exchange of bromine or chlorine for cyano, preference is givento using aromatic hydrocarbons as solvents. These preferably includebenzene, toluene, xylenes, etc. Particular preference is given to usingtoluene.

Compounds of the general formula (I) or (II) in which 1, 2, 3 or 4 ofthe Z¹, Z², Z³ or Z⁴ groups are S are obtainable from the correspondingcompounds of the formula (I) in which the Z¹, Z², Z³, Z⁴ groups are eachO, for example by reaction with the Davy or Lawesson reagent. Thegeneral conditions in the reaction with the Davy or Lawesson reagent areknown to those skilled in the art. The more precise conditions canoptionally be determined by means of simple preliminary experiments. Forexample, reference is made here to the article by A. Orzeszko et al.,“Investigation of the Thionation Reaction of Cyclic Imides”, Z.Naturforsch. 56b, 1035-1040, 2001, in which the exchange of the carbonyloxygen for sulfur on cyclic imides is investigated.

However, a preferred embodiment of the present invention relates tocompounds of the formula (I) in which the Z¹, Z², Z³ and Z⁴ radicals areeach O and to the use thereof.

Tetracarboximides of the formulae (I.Ba), (I.Bb1) and (I.Bb2) arepreparable by the process according to the invention proceeding from thecorresponding rylenetetracarboximides in which at least one of the R¹¹,R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals is hydrogen. Typically,the starting materials used for their preparation will, however, be therylenetetracarboxylic dianhydrides of the formula (II.A) which are knownper se.

Accordingly, the present invention further relates to processes forpreparing compounds of the formula (I.Ba)

in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have one of thedefinitions given above, in which

-   1) a rylene dianhydride of the formula (II.A)

-   -   in which    -   R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ are each selected from        hydrogen, Cl and CN,    -   where at least one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴        radicals is hydrogen, from 0 to 7 of the R¹¹, R¹², R¹³, R¹⁴,        R²¹, R²², R²³, R²⁴ radicals are each Cl and from 0 to 2 of the        R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ radicals are each CN,    -   is subjected to step a) and optionally step b) of the process        according to the invention, and

-   2) the compound obtained in step 1) is subjected to a reaction with    an amine of the formula R^(a)—NH₂ and optionally a different amine    of the formula R^(b)—NH₂.

Alternatively, the compounds of the formula (I.Ba) can be prepared by aprocess wherein

-   1′) a rylene dianhydride of the formula (II.A) is subjected first to    a reaction with an amine of the formula R^(a)—NH₂ and optionally a    different amine of the formula R^(b)—NH₂, and-   2′) the compound obtained in step 1′) is subjected to step a) and    optionally step b) of the process according to the invention.

The present invention further relates to a process for preparingcompounds of the formulae (I.Bb1) and/or (I.Bb2),

where R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ and X each have one ofthe definitions given above, in which

-   1″) a rylene dianhydride of the formula (II.A),

-   -   in which    -   R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ are each selected from        hydrogen, Cl and CN, and    -   where at least one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴        radicals is hydrogen, from 0 to 7 of the R¹¹, R¹², R¹³, R¹⁴,        R²¹, R²², R²³, R²⁴ radicals are each Cl and from 0 to 2 of the        R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ radicals are each CN,    -   is subjected to step a) and optionally step b) of the process        according to the invention, and

-   2″) the compound obtained in step 1″) is subjected to a reaction    with an amine of the formula H₂N—X—NH₂.

Alternatively, the compounds of the formulae (I.Bb1) and/or (I.Bb2) canbe prepared by a process in which

-   1′″) a rylene dianhydride of the formula (II.A) is subjected to a    reaction with an amine of the formula H₂N—X—NH₂, and-   2′″) the compound obtained in step 1′″) is subjected to step a) and    optionally to step b) of the process according to the invention.

The imidation of the carboxylic anhydride groups in reaction steps 2),1′), 2″) and 1′″) is known in principle and is described, for example,in DE 10 2004 007 382 A1. Preference is given to reacting thedianhydride with the primary amine in the presence of an aromaticsolvent such as toluene, xylene, mesitylene, phenol, or of a polaraprotic solvent. Suitable polar aprotic solvents are nitrogenheterocycles such as pyridine, pyrimidine, quinoline, isoquinoline,quinaldine, N-methylpiperidine, N-methylpiperidone andN-methylpyrrolidone. For reaction with an aromatic diamine of theformula H₂N—X—NH₂, preference is given to using a nitrogen heterocycleor phenol as a solvent. Suitable catalysts are those specified below.When phenol is used as the solvent, the catalyst used is preferablypiperazine.

The reaction can be undertaken in the presence of an imidation catalyst.Suitable imidation catalysts are organic and inorganic acids, forexample formic acid, acetic acid, propionic acid and phosphoric acid.Suitable imidation catalysts are also organic and inorganic salts oftransition metals, such as zinc, iron, copper and magnesium. Theseinclude, for example, zinc acetate, zinc propionate, zinc oxide,iron(II) acetate, iron(III) chloride, iron(II) sulfate, copper(II)acetate, copper(II) oxide and magnesium acetate. An imidation catalystis used preferably in the reaction of aromatic amines and is generallyalso advantageous for the reaction of cycloaliphatic amines. In thereaction of aliphatic amines, especially of short-chain aliphaticamines, it is generally possible to dispense with the use of animidation catalyst. The amount of the imidation catalyst used ispreferably from 5 to 80% by weight, more preferably from 10 to 75% byweight, based on the total amount of the compound to be imidated.

The molar ratio of amine to dianhydride is preferably from about 2:1 to10:1, more preferably from 2:1 to 4:1, for example from 2.2:1 to 3:1.

The organic acids mentioned above as imidation catalysts are alsosuitable as solvents.

The reaction temperature in steps 2), 1′), 2″) and 1′″) is generallyfrom ambient temperature to 200° C., preferably from 40 to 160° C.Aliphatic and cycloaliphatic amines are reacted preferably within atemperature range from about 60° C. to 100° C. Aromatic amines arereacted preferably within a temperature range from about 120 to 160° C.

Preference is given to effecting the reaction in reaction steps 2), 1′),2″) and 1′″) under a protective gas atmosphere, for example nitrogen.

Reaction steps 2), 1′), 2″) and 1′″) can be effected under standardpressure or, if desired, under elevated pressure. A suitable pressurerange is in the range from about 0.8 to 10 bar. When volatile amines(boiling point about 180° C.) are used, one preferred possibility is useunder elevated pressure.

The water formed in the reaction in steps 2), 1′), 2″) and 1′″) can beremoved by distillation by processes known to those skilled in the art.

In general, the diamines obtained in reaction step 2), 1′), 2″) and 1′″)can be used without further purification. For use of the products assemiconductors, it may, however, be advantageous to subject the productsto a further purification. This includes, for example, columnchromatography processes, in which case the products are preferablydissolved in a halogenated hydrocarbon such as methylene chloride or inan aromatic hydrocarbon, and subjected to a separation or filtration onsilica gel.

The inventive compounds and those obtainable by the process according tothe invention are particularly advantageously suitable as organicsemiconductors. They generally function as n-semiconductors. When thecompounds of the formula (I) used in accordance with the invention arecombined with other semiconductors and the position of the energy levelscauses the other semiconductors to function as n-semiconductors, thecompounds (I) may also function as p-semiconductors in exceptionalcases.

The compounds of the formula (I) are notable for their air stability.Moreover, they have a high charge transport mobility which clearly setsthem apart from known organic semiconductor materials. They additionallyhave a high on/off ratio.

The compounds of the formula (I) are particularly advantageouslysuitable for organic field-effect transistors. They may be used, forexample, for the production of integrated circuits (ICs), for whichcustomary n-channel MOSFETs (metal oxide semiconductor field-effecttransistors) have been used to date. These are then CMOS-likesemiconductor units, for example for microprocessors, microcontrollers,static RAM and other digital logic circuits. For the production ofsemiconductor materials, the compounds of the formula (I) can beprocessed further by one of the following processes: printing (offset,flexographic, gravure, screenprinting, inkjet, electrophotography),evaporation, laser transfer, photolithography, drop-casting. They areespecially suitable for use in displays (specifically large-surface areaand/or flexible displays) and RFID tags.

The compounds of the formula (I) are particularly advantageouslysuitable as electron conductors in organic field-effect transistors,organic solar cells and in organic light-emitting diodes. They are alsoparticularly advantageous as an exciton transport material in excitonicsolar cells.

The compounds of the formula (I) are also particularly advantageouslysuitable as fluorescent dyes in a display based on fluorescenceconversion. Such displays comprise generally a transparent substrate, afluorescent dye present on the substrate and a radiation source. Typicalradiation sources emit blue (color by blue) or UV light (color by uv).The dyes absorb either the blue or the UV light and are used as greenemitters. In these displays, for example, the red light is generated byexciting the red emitter by means of a green emitter which absorbs blueor UV light. Suitable color-by-blue displays are described, for example,in WO 98/28946. Suitable color-by-UV displays are described, forexample, by W. A. Crossland, I. D. Sprigle and A. B. Davey inPhotoluminescent LCDs (PL-LCD) using phosphors, Cambridge University andScreen Technology Ltd., Cambridge, UK. The compounds of the formula (I)are also particularly suitable in displays which, based on anelectrophoretic effect, switch colors on and off via charged pigmentdyes. Such electrophoretic displays are described, for example, in US2004/0130776.

The invention further provides organic field-effect transistorscomprising a substrate with at least one gate structure, a sourceelectrode and a drain electrode, and at least one compound of theformula (I) as defined above as a semiconductor, especially as ann-semiconductor.

The invention further provides substrates having a plurality of organicfield-effect transistors, wherein at least some of the field-effecttransistors comprise at least one compound of the formula (I) as definedabove as an n-semiconductor.

The invention also provides semiconductor units which comprise at leastone such substrate.

A specific embodiment is a substrate with a pattern (topography) oforganic field-effect transistors, each transistor comprising

-   -   an organic semiconductor disposed on the substrate;    -   a gate structure for controlling the conductivity of the        conductive channel; and    -   conductive source and drain electrodes at the two ends of the        channel,        the organic semiconductor consisting of at least one compound of        the formula (I) or comprising a compound of the formula (I). In        addition, the organic field-effect transistor generally        comprises a dielectric.

A further specific embodiment is a substrate having a pattern of organicfield-effect transistors, each transistor forming an integrated circuitor being part of an integrated circuit and at least some of thetransistors comprising at least one compound of the formula (I).

Suitable substrates are in principle the materials known for thispurpose. Suitable substrates comprise, for example, metals (preferablymetals of groups 8, 9, 10 or 11 of the Periodic Table, such as Au, Ag,Cu), oxidic materials (such as glass, ceramics, SiO₂, especiallyquartz), semiconductors (e.g. doped Si, doped Ge), metal alloys (forexample based on Au, Ag, Cu, etc.), semiconductor alloys, polymers (e.g.polyvinyl chloride, polyolefins such as polyethylene and polypropylene,polyesters, fluoropolymers, polyamides, polyimides, polyurethanes,polyalkyl(meth)acrylates, polystyrene and mixtures and compositesthereof), inorganic solids (e.g. ammonium chloride), paper andcombinations thereof. The substrates may be flexible or inflexible, andhave a curved or planar geometry, depending on the desired use.

A typical substrate for semiconductor units comprises a matrix (forexample a quartz or polymer matrix) and, optionally, a dielectric toplayer.

Suitable dielectrics are SiO₂, polystyrene, poly-α-methylstyrene,polyolefins (such as polypropylene, polyethylene, polyisobutene),polyvinylcarbazole, fluorinated polymers (e.g. Cytop), cyanopullulans(e.g. CYMM), polyvinylphenol, poly-p-xylene, polyvinyl chloride, orpolymers crosslinkable thermally or by atmospheric moisture. Specificdielectrics are “self-assembled nanodielectrics”, i.e. polymers whichare obtained from monomers comprising SiCl functionalities, for exampleCl₃SiOSiCl₃, Cl₃Si—(CH₂)₆—SiCl₃, Cl₃Si—(CH₂)₁₂—SiCl₃, and/or which arecrosslinked by atmospheric moisture or by addition of water diluted withsolvents (see, for example, Faccietti Adv. Mat. 2005, 17, 1705-1725).Instead of water, it is also possible for hydroxyl-containing polymerssuch as polyvinylphenol or polyvinyl alcohol or copolymers ofvinylphenol and styrene to serve as crosslinking components. It is alsopossible for at least one further polymer to be present during thecrosslinking operation, for example polystyrene, which is then alsocrosslinked (see Facietti, US patent application 2006/0202195).

The substrate may additionally have electrodes, such as gate, drain andsource electrodes of OFETs, which are normally localized on thesubstrate (for example deposited onto or embedded into a nonconductivelayer on the dielectric). The substrate may additionally compriseconductive gate electrodes of the OFETs, which are typically arrangedbelow the dielectric top layer (i.e. the gate dielectric).

In a specific embodiment, an insulator layer (gate insulating layer) ispresent on at least part of the substrate surface. The insulator layercomprises at least one insulator which is preferably selected frominorganic insulators such as SiO₂, Si₃N₄, etc., ferroelectric insulatorssuch as Al₂O₃, Ta₂O₅, La₂O₅, TiO₂, Y₂O₃, etc., organic insulators suchas polyimides, benzocyclobutene (BCB), polyvinyl alcohols,polyacrylates, etc., and combinations thereof.

Suitable materials for source and drain electrodes are in principleelectrically conductive materials. These include metals, preferablymetals of groups 6, 8, 9, 10 or 11 of the Periodic Table, such as Pd,Au, Ag, Cu, Al, Ni, Cr, etc. Also suitable are conductive polymers suchas PEDOT (=poly(3,4-ethylenedioxythiophene)):PSS(=poly(styrenesulfonate)), polyaniline, surface-modified gold, etc.Preferred electrically conductive materials have a specific resistanceof less than 10⁻³ ohm×meter, preferably less than 10⁻⁴ ohm×meter,especially less than 10⁻⁶ or 10⁻⁷ ohm×meter.

In a specific embodiment, drain and source electrodes are present atleast partly on the organic semiconductor material. It will beappreciated that the substrate may comprise further components as usedcustomarily in semiconductor materials or ICs, such as insulators,resistors, capacitors, conductor tracks, etc.

The electrodes may be applied by customary processes, such asevaporation, lithographic processes or another structuring process.

The semiconductor materials may also be processed with suitableauxiliaries (polymers, surfactants) in disperse phase by printing.

In a first preferred embodiment, the deposition of at least one compoundof the general formula (I) (and optionally further semiconductormaterials) is carried out by a gas phase deposition process (physicalvapor deposition, PVD). PVD processes are performed under high-vacuumconditions and comprise the following steps: evaporation, transport,deposition. It has been found that, surprisingly, the compounds of thegeneral formula (I) are suitable particularly advantageously for use ina PVD process, since they essentially do not decompose and/or formundesired by-products. The material deposited is obtained in highpurity. In a specific embodiment, the deposited material is obtained inthe form of crystals or comprises a high crystalline content. Ingeneral, for the PVD, at least one compound of the general formula (I)is heated to a temperature above its evaporation temperature anddeposited on a substrate by cooling below the crystallizationtemperature. The temperature of the substrate in the deposition ispreferably within a range from about 20 to 250° C., more preferably from50 to 200° C. It has been found that, surprisingly, elevated substratetemperatures in the deposition of the compounds of the formula (I) canhave advantageous effects on the properties of the semiconductorelements achieved.

The resulting semiconductor layers generally have a thickness which issufficient for ohmic contact between source and drain electrodes. Thedeposition can be effected under an inert atmosphere, for example, undernitrogen, argon or helium.

The deposition is effected typically at ambient pressure or underreduced pressure. A suitable pressure range is from about 10⁻⁷ to 1.5bar.

The compound of the formula (I) is preferably deposited on the substratein a thickness of from 10 to 1000 nm, more preferably from 15 to 250 nm.In a specific embodiment, the compound of the formula (I) is depositedat least partly in crystalline form. For this purpose, especially theabove-described PVD process is suitable. Moreover, it is possible to usepreviously prepared organic semiconductor crystals. Suitable processesfor obtaining such crystals are described by R. A. Laudise et al. in“Physical Vapor Growth of Organic Semi-Conductors”, Journal of CrystalGrowth 187 (1998), pages 449-454, and in “Physical Vapor Growth ofCentimeter-sized Crystals of α-Hexathiophene”, Journal of Crystal Growth1982 (1997), pages 416-427, which are incorporated here by reference.

In a second preferred embodiment, the deposition of at least onecompound of the general formula (I) (and optionally furthersemiconductor materials) is effected by spin-coating. Surprisingly, itis thus also possible to use the compounds of the formula (I) used inaccordance with the invention in a wet processing method to producesemiconductor substrates. The compounds of the formula (I) should thusalso be suitable for producing semiconductor elements, especially OFETsor based on OFETs, by a printing process. It is possible for thispurpose to use customary printing processes (inkjet, flexographic,offset, gravure; intaglio printing, nanoprinting). Preferred solventsfor the use of compounds of the formula (I) in a printing process arearomatic solvents such as toluene, xylene, etc. It is also possible toadd thickening substances such as polymers, for example polystyrene,etc., to these “semiconductor inks”. In this case, the dielectrics usedare the aforementioned compounds.

In a preferred embodiment, the inventive field-effect transistor is athin-film transistor (TFT). In a customary construction, a thin-filmtransistor has a gate electrode disposed on the substrate, a gateinsulation layer disposed thereon and on the substrate, a semiconductorlayer disposed on the gate insulator layer, an ohmic contact layer onthe semiconductor layer, and a source electrode and a drain electrode onthe ohmic contact layer.

In a preferred embodiment, the surface of the substrate, before thedeposition of at least one compound of the general formula (I) (andoptionally of at least one further semiconductor material), is subjectedto a modification. This modification serves to form regions which bindthe semiconductor materials and/or regions on which no semiconductormaterials can be deposited. The surface of the substrate is preferablymodified with at least one compound (C1) which is suitable for bindingto the surface of the substrate and to the compounds of the formula (I).In a suitable embodiment, a portion of the surface or the completesurface of the substrate is coated with at least one compound (C1) inorder to enable improved deposition of at least one compound of thegeneral formula (I) (and optionally further semiconductive compounds). Afurther embodiment comprises the deposition of a pattern of compounds ofthe general formula (C1) on the substrate by a corresponding productionprocess. These include the mask processes known for this purpose andso-called “patterning” processes, as described, for example, in U.S.Ser. No. 11/353,934, which is incorporated here fully by reference.

Suitable compounds of the formula (C1) are capable of a bindinginteraction both with the substrate and with at least one semiconductorcompound of the general formula (I). The term “binding interaction”comprises the formation of a chemical bond (covalent bond), ionic bond,coordinative interaction, van der Waals interactions, e.g. dipole-dipoleinteractions etc.), and combinations thereof. Suitable compounds of thegeneral formula (C1) are:

-   -   silane, phosphonic acids, carboxylic acids, hydroxamic acids,        such as alkyltrichlorosilanes, e.g. n-octadecyltrichlorosilane;        compounds with trialkoxysilane groups, e.g.        alkyltrialkoxysilanes such as n-octadecyltrimethoxysilane,        n-octadecyltriethoxysilane, n-octadecyltri(n-propyl)oxysilane,        n-octadecyltri(isopropyl)oxysilane; trialkoxyaminoalkylsilanes        such as triethoxyaminopropylsilane and        N-[(3-triethoxysilyl)propyl]ethylenediamine; trialkoxyalkyl        3-glycidyl ether silanes such as triethoxypropyl 3-glycidyl        ether silane; trialkoxyallylsilanes such as        allyltrimethoxysilane; trialkoxy(isocyanatoalkyl)silanes;        trialkoxysilyl(meth)acryloyloxyalkanes and        trialkoxysilyl(meth)acrylamidoalkanes such as        1-triethoxysilyl-3-acryloyloxypropane.    -   amines, phosphines and sulfur-comprising compounds, especially        thiols.

The compound (C1) is preferably selected from alkyltrialkoxysilanes,especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane;hexaalkyldisilazanes, and especially hexamethyldisilazane (HMDS);C₈-C₃₀-alkylthiols, especially hexadecanethiol; mercaptocarboxylic acidsand mercaptosulfonic acids, especially mercaptoacetic acid,3-mercaptopropionic acid, mercaptosuccinic acid,3-mercapto-1-propanesulfonic acid and the alkali metal and ammoniumsalts thereof.

Various semiconductor architectures comprising the inventivesemiconductors are also conceivable, for example top contact, top gate,bottom contact, bottom gate, or else a vertical construction, forexample a VOFET (vertical organic field-effect transistor), asdescribed, for example, in US 2004/0046182.

The layer thicknesses are, for example, from 10 nm to 5 μm insemiconductors, from 50 nm to 10 μm in the dielectric; the electrodesmay, for example, be from 20 nm to 1 μm. The OFETs may also be combinedto form other components such as ring oscillators or inverters.

A further aspect of the invention is the provision of electroniccomponents which comprise a plurality of semiconductor components, whichmay be n- and/or p-semiconductors. Examples of such components arefield-effect transistors (FETs), bipolar junction transistors (BJTs),tunnel diodes, converters, light-emitting components, biological andchemical detectors or sensors, temperature-dependent detectors,photodetectors such as polarization-sensitive photodetectors, gates,AND, NAND, NOT, OR, TOR and NOR gates, registers, switches, timer units,static or dynamic stores and other dynamic or sequential, logical orother digital components including programmable switches.

A specific semiconductor element is an inverter. In digital logic, theinverter is a gate which inverts an input signal. The inverter is alsoreferred to as a NOT gate. Real inverter switches have an output currentwhich constitutes the opposite of the input current. Typical values are,for example, (0, +5V) for TTL switches. The performance of a digitalinverter reproduces the voltage transfer curve (VTC), i.e. the plot ofinput current against output current. Ideally, it is a staged functionand, the closer the real measured curve approximates to such a stage,the better the inverter is. In a specific embodiment of the invention,the compounds of the formula (I) are used as organic n-semiconductors inan inverter.

The compounds of the formula (I) are also particularly advantageouslysuitable for use in organic photovoltaics (OPVs). These compounds arepreferably suitable for use in solar cells which are characterized bydiffusion of excited states (exciton diffusion). In this case, one orboth of the semiconductor materials utilized is notable for a diffusionof excited states (exciton mobility). Also suitable is the combinationof at least one semiconductor material which is characterized bydiffusion of excited states with polymers which permit conduction of theexcited states along the polymer chain. In the context of the invention,such solar cells are referred to as excitonic solar cells. The directconversion of solar energy to electrical energy in solar cells is basedon the internal photo effect of a semiconductor material, i.e. thegeneration of electron-hole pairs by absorption of photons and theseparation of the negative and positive charge carriers at a p-ntransition or a Schottky contact. An exciton can form, for example, whena photon penetrates into a semiconductor and excites an electron totransfer from the valence band into the conduction band. In order togenerate current, the excited state generated by the absorbed photonsmust, however, reach a p-n transition in order to generate a hole and anelectron which then flow to the anode and cathode. The photovoltage thusgenerated can bring about a photocurrent in an external circuit, throughwhich the solar cell delivers its power. The semiconductor can absorbonly those photons which have an energy which is greater than its bandgap. The size of the semiconductor band gap thus determines theproportion of sunlight which can be converted to electrical energy.Solar cells consist normally of two absorbing materials with differentband gaps in order to very effectively utilize the solar energy. Mostorganic semiconductors have exciton diffusion lengths of up to 10 nm.There is still a need here for organic semiconductors through which theexcited state can be passed on over very large distances. It has nowbeen found that, surprisingly, the compounds of the general formula (I)described above are particularly advantageously suitable for use inexcitonic solar cells.

Suitable organic solar cells generally have a layer structure andgenerally comprise at least the following layers: anode, photoactivelayer and cathode. These layers generally consist of a substratecustomary therefor. The structure of organic solar cells is described,for example, in US 2005/0098726 A1 and US 2005/0224905 A1, which arefully incorporated here by reference.

Suitable substrates are, for example, oxidic materials (such as glass,ceramic, SiO₂, especially quartz, etc.), polymers (e.g. polyvinylchloride, polyolefins such as polyethylene and polypropylene,polyesters, fluoropolymers, polyamides, polyurethanes,polyalkyl(meth)acrylates, polystyrene and mixtures and compositesthereof) and combinations thereof.

Suitable electrodes (cathode, anode) are in principle metals (preferablyof groups 2, 8, 9, 10, 11 or 13 of the Periodic Table, e.g. Pt, Au, Ag,Cu, Al, In, Mg, Ca), semiconductors (e.g. doped Si, doped Ge, indium tinoxide (ITO), gallium indium tin oxide (GITO), zinc indium tin oxide(ZITO), etc.), metal alloys (e.g. based on Pt, Au, Ag, Cu, etc.,especially Mg/Ag alloys), semiconductor alloys, etc. The anode used ispreferably a material essentially transparent to incident light. Thisincludes, for example, ITO, doped ITO, ZnO, TiO₂, Ag, Au, Pt. Thecathode used is preferably a material which essentially reflects theincident light. This includes, for example, metal films, for example ofAl, Ag, Au, In, Mg, Mg/Al, Ca, etc.

For its part, the photoactive layer comprises at least one or consistsof at least one layer which comprises, as an organic semiconductormaterial, at least one compound which is selected from compounds of theformula (I) as defined above. In one embodiment, the photoactive layercomprises at least one organic acceptor material. In addition to thephotoactive layer, there may be one or more further layers, for examplea layer with electron-conducting properties (ETL, electron transportlayer) and a layer which comprises a hole-conducting material (holetransport layer, HTL) which need not absorb, exciton- and hole-blockinglayers (e.g. EBLs) which should not absorb, multiplication layers.Suitable exciton- and hole-blocking layers are described, for example,in U.S. Pat. No. 6,451,415.

Suitable exciton blocker layers are, for example, bathocuproins (BCPs),4,4′,4″-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) orpolyethylenedioxythiophene (PEDOT), as described in U.S. Pat. No.7,026,041.

The inventive excitonic solar cells are based on photoactivedonor-acceptor heterojunctions. When at least one compound of theformula (I) is used as the HTM (hole transport material), thecorresponding ETM (exciton transport material) must be selected suchthat, after excitation of the compounds, a rapid electron transfer tothe ETM takes place. Suitable ETMs are, for example, C60 and otherfullerenes, perylene-3,4:9,10-bis(dicarboximides) (PTCDIs), etc. When atleast one compound of the formula (I) is used as the ETM, thecomplementary HTM must be selected such that, after excitation, a rapidhole transfer to the HTM takes place. The heterojunction may have a flatconfiguration (cf. Two layer organic photovoltaic cell, C. W. Tang,Appl. Phys. Lett., 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J.Holzäpfel, J. Marktanner, M. Möbus, F. Stölzle, Mol. Cryst. Liq. Cryst.,252, 243-258 (1994).) or be implemented as a bulk heterojunction (orinterpenetrating donor-acceptor network; cf., for example, C. J. Brabec,N. S. Sariciftci, J. C. Hummelen, Adv. Funct. Mater., 11 (1), 15(2001).). The photoactive layer based on a heterojunction between atleast one compound of the formula (I) and an HTL (hole transport layer)or ETL (exciton transport layer) can be used in solar cells with MiM,pin, pn, Mip or Min structure (M=metal, p=p-doped organic or inorganicsemiconductor, n=n-doped organic or inorganic semiconductor,i=intrinsically conductive system of organic layers; cf., for example,J. Drechsel et al., Org. Eletron., 5 (4), 175 (2004) or Maennig et al.,Appl. Phys. A 79, 1-14 (2004)). It can also be used in tandem cells, asdescribed by P. Peumnas, A. Yakimov, S. R. Forrest in J. Appl. Phys, 93(7), 3693-3723 (2003) (cf. U.S. Pat. No. 4,461,922, U.S. Pat. No.6,198,091 and U.S. Pat. No. 6,198,092). It can also be used in tandemcells composed of two or more MiM, pin, Mip or Min diodes stacked on oneanother (cf. patent application DE 103 13 232.5) (J. Drechsel et al.,Thin Solid Films, 451452, 515-517 (2004)).

Thin layers of the compounds and of all other layers can be produced byvapor deposition under reduced pressure or in inert gas atmosphere, bylaser ablation or by solution- or dispersion-processible methods such asspin-coating, knife-coating, casting methods, spraying, dip-coating orprinting (e.g. inkjet, flexographic, offset, gravure; intaglio,nanoimprinting). The layer thicknesses of the M, n, i and p layers aretypically from 10 to 1000 nm, preferably from 10 to 400 nm.

The substrates used are, for example, glass, metal foils or polymerfilms which are generally coated with a transparent conductive layer(for example SnO₂:F, SnO₂:In, ZnO:Al, carbon nanotubes, thin metallayers).

In addition to the compounds of the general formula (I), the followingsemiconductor materials are suitable for use in organic photovoltaics:

Phthalocyanines, such as hexadecachlorophthalocyanines andhexadecafluorophthalocyanines, metal-free phthalocyanines andphthalocyanines comprising divalent metals or metal atom-containinggroups, especially those of titanyloxy, vanadyloxy, iron, copper, zinc,etc. Suitable phthalocyanines are especially copper phthalocyanine, zincphthalocyanine, metal-free phthalocyanine, copperhexadecachlorophthalocyanine, zinc hexadecachlorophthalocyanine,metal-free hexadecachlorophthalocyanine, copperhexadecafluorophthalocyanine, hexadecafluorophthalocyanine or metal-freehexadecafluorophthalocyanine.

Porphyrins, for example 5,10,15,20-tetra(3-pyridyl)porphyrin (TpyP), orelse tetrabenzoporphyrins, for example metal-free tetrabenzoporphyrin,copper tetrabenzoporphyrin or zinc tetrabenzoporphyrin.

Liquid-crystalline (LC) materials, for example coronenes, such ashexabenzocoronene (HBC-PhC12), coronenediimides, or triphenylenes suchas 2,3,6,7,10,11-hexahexylthiotriphenylene (HTT₆),2,3,6,7,10,11-hexakis(4-n-nonylphenyl)triphenylene (PTP₉) or2,3,6,7,10,11-hexakis(undecyloxy)triphenylene (HAT₁₁). Particularpreference is given to liquid-crystalline materials which are discotic.

Thiophenes, oligothiophenes and substituted derivatives thereof.Suitable oligothiophenes are quaterthiophenes, quinquethiophenes,sexithiophenes, α,ω-di(C₁-C₈)alkyloligothiophenes such asα,ω-dihexylquaterthiophenes, α,ω-dihexylquinquethiophenes andα,ω-dihexylsexithiophenes, poly(alkylthiophenes) such aspoly(3-hexylthiophene), bis(dithienothiophenes), anthradithiophenes anddialkylanthradithiophenes such as dihexylanthradithiophene,phenylene-thiophene (P-T) oligomers and derivatives thereof, especiallyα,ω-alkyl-substituted phenylenethiophene oligomers.

Also suitable are compounds of theα,α′-bis(2,2-dicyanovinyl)quinquethiophene (DCV₅T) type,poly[3-(4-octylphenyl)-2,2′-bithiophene] (PTOPT),poly(3-(4′-(1,4,7-trioxaoctyl)phenyl)thiophene (PEOPT),poly(3-(2′-methoxy-5′-octylphenyl)thiophene) (POMeOPT),poly(3-octylthiophene) (P3OT), poly(pyridopyrazinevinylene)polythiopheneblends such as EHH-PpyPz, PTPTB copolymers, BBL,poly(9,9-dioctylfluorene-co-bis-N,N′-(4-methoxyphenyl)bis-N,N′-phenyl-1,4-phenylenediamine)(PFMO); see Brabec C., Adv. Mater., 2996, 18, 2884, (PCPDTBT)poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-4,7-(2,1,3-benzothiadiazole);

Paraphenylenevinylene and paraphenylenevinylene-comprising oligomers andpolymers, for example polyparaphenylenevinylene (PPV), MEH-PPV(poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene)), MDMO-PPV(poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene)),cyano-paraphenylenevinylene (CN-PPV), CN-PPV modified with variousalkoxy groups;

Phenyleneethynylene/phenylenevinylene hybrid polymers (PPE-PPV).

Polyfluorenes and alternating polyfluorene copolymers, for example with4,7-dithien-2′-yl-2,1,3-benzothiadiazole. Also suitable arepoly(9,9′-dioctylfluorene-co-benzothiadiazole) (F₈BT),poly(9,9′-dioctylfluorene-co-bis(N,N′-(4-butylphenyl))bis(N,N′-phenyl)-1,4-phenylenediamine(PFB).

Polycarbazoles, i.e. carbazole-comprising oligomers and polymers, suchas (2,7) and (3,6).

Polyanilines, i.e. aniline-comprising oligomers and polymers.

Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles,polyfurans, polysiloles, polyphospholes,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (TPD),4,4′-bis(carbazol-9-yl)biphenyl (CBP),2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene(Spiro-MeOTAD).

Fullerenes, especially C60 and derivatives thereof such as PCBM(=[6,6]-phenyl-C₆₁-butyric acid methyl ester). In such case, thefullerene derivative is a hole conductor.

All aforementioned semiconductor materials may also be doped. Examplesof suitable dopants for n-semiconductors are, for example, the compoundsof the formula (I), rhodamine or pyronin B. Examples of suitable dopantsfor p-semiconductors are2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ).

The invention further provides an organic light-emitting diode (OLED)which comprises at least one compound of the general formula (I) asdefined above. The compounds of the formula (I) may serve as a chargetransport material (electron conductor).

Organic light-emitting diodes are in principle constructed from severallayers. These include 1. anode 2. hole-transporting layer 3.light-emitting layer 4. electron-transporting layer 5. cathode. It isalso possible that the organic light-emitting diode does not have all ofthe layers mentioned; for example, an organic light-emitting diode withthe layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) islikewise suitable, in which case the functions of the layers (2)(hole-transporting layer) and (4) (electron-transporting layer) areassumed by the adjacent layers. OLEDs which have the layers (1), (2),(3) and (5) or the layers (1), (3), (4) and (5) are likewise suitable.The structure of organic light-emitting diodes and processes for theirproduction are known in principle to those skilled in the art, forexample from WO 2005/019373. Suitable materials for the individuallayers of OLEDs are disclosed, for example, in WO 00/70655. Reference ismade here to the disclosure of these documents. Inventive OLEDs can beproduced by methods known to those skilled in the art. In general, anOLED is produced by successive vapor deposition of the individual layersonto a suitable substrate. Suitable substrates are, for example, glassor polymer films. For vapor deposition, it is possible to use customarytechniques such as thermal evaporation, chemical vapor deposition andothers. In an alternative process, the organic layers may be coated fromsolutions or dispersions in suitable solvents, for which coatingtechniques known to those skilled in the art are employed. Compositionswhich, as well as a compound of the general formula (I) have a polymericmaterial in one of the layers of the OLED, preferably in thelight-emitting layer, are generally applied as a layer by processingfrom solution.

As a result of the inventive use of the compounds (I), it is possible toobtain OLEDs with high efficiency. The inventive OLEDs can be used inall devices in which electroluminescence is useful. Suitable devices arepreferably selected from stationary and mobile visual display units.Stationary visual display units are, for example, visual display unitsof computers, televisions, visual display units in printers, kitchenappliances and advertising panels, illuminations and information panels.Mobile visual display units are, for example, visual display units incellphones, laptops, digital cameras, vehicles and destination displayson buses and trains. Moreover, the compounds (I) may be used in OLEDswith inverse structure. The compounds (I) in these inverse OLEDs are inturn preferably used in the light-emitting layer. The structure ofinverse OLEDs and the materials typically used therein are known tothose skilled in the art.

Before they are used as charge transport materials or exciton transportmaterials, it may be advisable to subject the compounds of the formula(I) to a purification process. Suitable purification processes compriseconversion of the compounds of the formula (I) to the gas phase. Thisincludes purification by sublimation or PVD (physical vapor deposition).Preference is given to a fractional sublimation. For fractionalsublimation and/or deposition of the compound, a temperature gradient isused. Preference is given to subliming the compound of the formula (I)with heating in a carrier gas stream. The carrier gas then flows througha separating chamber. A suitable separating chamber has at least twodifferent separating zones with different temperatures. Preference isgiven to using a three-zone furnace. A suitable process and an apparatusfor fractional sublimation is described in U.S. Pat. No. 4,036,594.

The invention further provides a process for depositing at least onecompound of the formula (I) onto or applying at least one compound ofthe formula (I) to a substrate by a gas phase deposition process or awet application process.

The invention is illustrated in detail with reference to the followingnonrestrictive examples.

EXAMPLES Synthesis Examples Example 1 Preparation ofoctafluoro-N,N′-dimethylperylene-3,4:9,10-tetracarboximide 1.a)Preparation ofoctachloro-N,N′-dimethylperylene-3,4:9,10-tetracarboximide

To a solution of N,N′-dimethylperylene-3,4:9,10-tetracarboximide (20.9g, 0.05 mol) in chlorosulfonic acid (200 g) was introduced, at 80° C.over a period of 28 hours, chlorine (approx. 500 g). Over this period,iodine (10 g) was added in portions. The resulting reaction mixture wascooled and added to ice-water. The solid which precipitated out wasfiltered off and washed until the filtrate was pH-neutral. After dryingunder reduced pressure,octachloro-N,N′-dimethylperylene-3,4:9,10-tetracarboximide was obtainedas an orange solid (28.8 g; 83% yield).

The compound was purified further by recrystallization from toluene. Tothis end, 4.0 g of the crude product in toluene (1.11) were heated underreflux and cooled to 0° C. for several days. The precipitated solid wasfiltered off and dried under reduced pressure. This afforded 3.21 g ofthe purified compound.

1.b) Preparation ofoctafluoro-N,N-dimethylperylene-3,4:9,10-tetracarboximide

To a mixture of sulfolane (250 ml), 18-crown-6 ether (11.4 g, 43.2 mmol)and potassium fluoride (7.3 g, 125 mmol) was added, at 180° C.,N,N′-dimethyl-octachloroperylene-3,4:9,10-tetracarboximide (3.1 g, 5mmol). The reaction mixture was stirred at this temperature for onefurther hour. After cooling to room temperature, demineralized water wasadded. The solid which precipitated out was filtered off and washed withdemineralized water and dried. The resulting product was purified bycolumn chromatography (SiO₂, toluene/ethyl acetate, 10:1).Octafluoro-N,N-dimethylperylene-3,4:9,10-tetracarboximide was obtainedas a brownish-yellow solid in an amount of 45 mg (1.5% yield).

R_(f) (toluene/ethyl acetate; 10:1)=0.19.

λ_(max emission) (high dilution, CH₂Cl₂)=481 nm, 515 nm

λ_(max absorption) (CH₂Cl₂)=approx. 408 nm (20.9 l/g cm), 435 nm (47.9l/g cm), 466 nm (approx. 65.8 l/g cm)

1.c) Alternative route to the preparation ofoctafluoro-N,N-dimethylperylene-3,4:9,10-tetracarboximide

To a mixture of 166 ml of o-xylene, 1.7 g (6.7 mmol) of(N,N′-dimethylimidazolidino)tetramethylguanidinium chloride and 30.0 g(533 mmol) of potassium fluoride were added 4.63 g (6.7 mmol) ofoctachloro-N,N′-dimethylperylene-3,4:9,10-tetracarboximide from example1a. The reaction mixture was heated at reflux for 30 minutes.Thereafter, the reaction mixture was allowed to cool to room temperatureand the product was isolated directly from the reaction mixture bycolumn chromatography on 180 g of silica gel using petroleum ether anddichloromethane. After repeated chromatography, 1.55 g (41%) of thetitle compound were obtained with a purity of 98%, and 0.6 g (16%) ofthe title compound with a purity of 94%.

The title compound was obtained in very high purity by repeatedchromatography with a flow rate of 101 l/g with UV/VIS detection at 469nm.

Example 2 Preparation of octachloroperylene-3,4:9,10-tetracarboximide

To a solution of perylene-3,4:9,10-tetracarboximide (19.5 g, 0.05 mol)in chlorosulfonic acid (200 g) was added iodine (2.0 g). The reactionmixture was heated to 80° C. Over a period of 25 hours, chlorine(approx. 445 g) was introduced. After cooling to room temperature, thereaction mixture was added to ice. The solid which precipitated out wasfiltered off and washed repeatedly with water. After drying underreduced pressure,octachloro-N,N′-dihydroperylene-3,4:9,10-tetracarboximide was obtainedas an orange solid in an amount of 26.14 g (79% yield).

The product was purified further by recrystallization. To this end, 4.0g of the crude product were dissolved in N-methylpyrrolidone (NMP, 70ml) at 140° C., and the mixture was cooled slowly to room temperature.The precipitate was isolated by filtration, washed with petroleum etherand dried under reduced pressure. Subsequently, the residue was taken upin acetic acid for several days and stirred under reflux conditions.

After another filtration and drying, 0.81 g of purifiedoctachloro-N,N′-dihydroperylene-3,4:9,10-tetracarboximide was obtained(chlorine content: 42.7% (theor.: 42.6%)).

Example 3 Preparation of perchloroperylene-3,4:9,10-tetracarboxylicdianhydride

To a solution of perylene-3,4:9,10-tetracarboxylic anhydride (20.0 g) inchlorosulfonic acid (200 g) was added iodine (1.0 g). The reactionmixture was heated to 60° C. Over a period of 7 hours, chlorine (approx.120 g) was introduced. Subsequently, iodine (1.0 g) was added again, themixture was heated to 80° C. and further chlorine was introduced over aperiod of 5 hours. After cooling to room temperature, the reactionmixture was poured onto ice-water. The solid which precipitated out wasfiltered off and washed until the filtrate was pH-neutral. After dryingunder reduced pressure, octachloroperylene-3,4:9,10-tetracarboxylicanhydride was obtained as an orange solid (29.8 g; 89% yield).

Example 4 Preparation of Compounds (4.a) and (4.b)

A mixture of 1.8-diaminonapthalene (1.78 g, 11.25 mmol), pyrazine (0.9g, 11.25 mmol) and perchloroperylene-3,4:9,10-tetracarboxylic anhydride(3.0 g, 4.5 mmol) in phenol (50 g) was stirred at a temperature of 120°C. for 36 hours. Subsequently, the reaction mixture was cooled to roomtemperature and admixed with methanol. The solid was filtered off,washed repeatedly with methanol and dilute hydrochloric acid and thendried. A mixture of the compounds (4.a) and (4.b) was obtained as ablack solid in an amount of 3.97 g (quantitative yield).

Example 5 Preparation ofoctachloro-N,N′-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-tetracarboximide

A mixture of octachloroperylene-3,4:9,10-tetracarboxylic dianhydride(1.0 g, 1.5 mmol) and 2,6-diisopropylaniline (6 mmol) in propionic acid(16 ml) was stirred at a temperature of 100° C. for 5 hours. Aftercooling to room temperature, the reaction mixture was admixed withwater. The solid which precipitated out was filtered off and dried underreduced pressure. The crude product thus obtained was purified by columnchromatography (SiO₂, dichloromethane).Octachloro-N,N′-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-tetracarboximidewas obtained as an orange solid in an amount of 0.6 g (40% yield). R_(f)(SiO₂, toluene/ethyl acetate, 10:1)=0.86.

Example 6 Preparation ofoctachloro-N,N′-bis(1H,1H-perfluorobutyl)perylene-3,4:9,10-tetracarboximide6.a) Preparation ofN,N′-bis(1H,1H-perfluorobutyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboximide(not inventive)

A mixture of 1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylicdianhydride (9.38 g, 17.7 mmol) and 1H,1H-heptafluoro-n-butylamine (9.88g, 49.6 mmol) in N-methylpyrrolidone (NMP, 100 ml) and acetic acid (6.4g, 106 mmol) was stirred at a temperature of 90° C. for 5 h. Aftercooling to room temperature, the reaction mixture was added to dilutehydrochloric acid (250 ml). The solid which precipitated out wasfiltered off, washed with water until the filtrate was pH-neutral anddried under reduced pressure. This afforded an orange solid (14.3 g),which was purified by column chromatography (SiO₂, toluene/acetone).

N,N′-bis(1H,1H-perfluorobutyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboximidewas obtained as a product mixture with the corresponding trichlorinatedperylene, as an orange solid, in an amount of 12.83 g (81% yield). R_(f)(toluene)=0.39.

6.b) Preparation ofoctachloro-N,N′-bis(1H,1H-perfluorobutyl)perylene-3,4:9,10-tetracarboximide

The product mixture obtained under 6.a) (19.0 g, 21 mmol) inchlorosulfonic acid (200 g) was admixed with iodine (1.0 g) and heated.At a temperature of 60° C., an excess of chlorine was introduced intothe reaction mixture at standard pressure over a period of 7 hours. Overthis period, further iodine (1.0 g) was added in portions. After coolingto room temperature, the reaction mixture was added to ice. The solidwhich precipitated out was filtered off and washed with water. Thisafforded 21.8 g (quant. yield) of a toluene-soluble, orange solid(chlorine content: 28.3% (theor.: 27.5%)).

Example 7 Preparation oftetrachlorotetrafluoro-N,N-dimethylperylene-3,4:9,10-tetracarboximide

To a mixture of 150 ml of ortho-xylene, 0.75 g (3 mmol) of(N,N′-dimethylimidazolidino)tetramethylguanidinium chloride and 14.0 g(240 mmol) of potassium fluoride were added 2.08 g (3 mmol) ofoctachloro-N,N′-dimethylperylene-3,4:9,10-tetracarboximide from example1.a, and the reaction mixture was heated to 80° C. The mixture wasstirred at this temperature for four hours and then cooled to roomtemperature. The reaction mixture was added directly to a frit filledwith silica gel, and the xylene was washed out with petroleum ether.Subsequently, the product was eluted with 10:1 methylenechloride/tert-butyl methyl ether to obtain 0.62 g (53%) of a brownishsolid.

Example 8 Preparation ofoctafluoro-N,N′-bis(1H,1H-perfluorobutyl)perylene-3,4:9,10-tetracarboximide

To a mixture of 70 ml of dry xylene, 1.06 g (4 mmol) of 18-crown-6 and4.65 g (80 mmol) of potassium fluoride was added 0.515 g (0.5 mmol) ofoctachloro-N,N′-bis(1H,1H-perfluorobutyl)perylene-3,4:9,10-tetracarboximide(compound from example 6.b) at 40° C. After stirring at this temperaturefor 1.5 hours, the mixture was heated to 80° C., stirred at thistemperature for 30 minutes, then heated to 120° C. and stirred at thistemperature for 30 minutes, before heating to reflux temperature. Thereaction mixture was heated under reflux for two hours. Thereafter, thereaction mixture was cooled and filtered, the residue was washed withtoluene and the filtrate was concentrated. The product was purified bychromatography with dichloromethane to obtain 79 mg (18%) of a brownishpowder. R_(f) (dichloromethane)=0.28;

MALDI-MS: M⁻=897.898:

Example 9 Preparation oftetrachlorotetrafluoro-N,N′-bis(1H,1H-perfluorobutyl)perylene-3,4:9,10-tetracarboximide

To a mixture of 100 ml of anhydrous xylene, 0.25 g (1 mmol) of(N,N′-dimethylimidazolidino)tetramethylguanidinium chloride and 4.65 g(80 mmol) of potassium fluoride were added 1.03 g ofoctafluoro-N,N-dimethylperylene-3,4;9,10-tetracarboximide (compound fromexample 6.b). The reaction mixture was heated to 120° C. and kept atthis temperature for 30 minutes. After cooling to room temperature,potassium fluoride was filtered off and washed with dichloromethane andpetroleum ether. The resulting solution was purified by chromatographyon silica gel using petroleum ether and tert-butyl methyl ether.

R_(f) (CH₂Cl₂)=0.49;

MALDI-MS: M⁻=961.8 g/mol.

Example 10 Preparation ofoctafluoro-N,N′-(2,6-diisopropylphenyl)perylene-3,4:9,10-tetracarboximide

To a mixture of 35 ml of o-xylene, 0.25 g (1 mmol) of(N,N′-dimethylimidazolidino)tetramethylguanidinium chloride and 4.5 g(80 mmol) of potassium fluoride was added 1.0 g (1.02 mmol) ofoctachloro-N,N′-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-tetracarboximide(compound from example 5). The reaction mixture was heated at reflux forone hour, then cooled and purified by chromatography on toluene.

R_(f) (toluene:ethyl acetate 10:1)=0.6.

Example 11 Preparation ofN,N′-bis(3,5-trifluoromethylphenyl)perchloroperylene-3,4:9,10-tetracarboximide11.a: Preparation ofN,N′-bis(3,5-trifluoromethylphenyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboximide(noninventive)

A mixture of 10.6 g (20 mmol) of1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic dianhydride, 100ml of NMP, 12.8 g (56 mmol) of 3,5-bis(trifluoromethyl)aniline and 7.2 g(120 mmol) of acetic acid was heated to 90° C. for approx. 70 hours. Thereaction mixture was allowed to cool and then poured onto 1000 ml ofdilute hydrochloric acid, and the precipitate was filtered off, washedwith water and dried under reduced pressure. The product was purified bychromatography on silica gel using a mixture of toluene and petroleumether employing a concentration gradient. This gave 8.52 g (45%) of anorange powder.

R_(f) (1:1 toluene:dichloromethane)=0.67

11.b: Preparation ofN,N′-bis(3,5-trifluoromethylphenyl)perchloroperylene-3,4:9,10-tetracarboximide

A mixture of 7.9 g of the compound from 11.a, 95.0 g (55 ml) ofchlorosulfonic acid and 0.5 g of iodine was heated to 60° C. 53.0 g ofchlorine were introduced under the surface of the mixture and themixture was stirred at 60° C. for 3 hours and at room temperature for 48hours. The mixture was poured onto ice, filtered and washed toneutrality with water. This gave 7.3 g of an orange crude product. 3.0 gof the crude product were purified by column chromatography (column witha diameter of 6.5 cm) on 180 g of silica gel using 1.5:1 petroleumether/dichloromethane. This gave 0.93 g of pure title compound. R_(f)(toluene)=0.61

Example 12 Preparation of N,N′-bis(1,H, 1H, 2H,2′H-perfluorodecyl)octachloroperylene-3,4:9,10-tetracarboximide 12.a:Preparation of N,N′-bis(1,H,1′H,2H,2′H-perfluorodecyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboximide(noninventive)

The compound was prepared analogously to the process in example 6.a.

12. b: Preparation of N,N′-bis(1,H, 1′H, 2H,2′H-perfluorodecyl)octachloroperylene-3,4:9,10-tetracarboximide

The chlorination was effected analogously to example 11.b, except that atotal of 212 g of chlorine were introduced in portions at 60° C. over aperiod of four days. The reaction mixture was added to ice-water,filtered, washed to neutrality with water and dried under reducedpressure. 6.0 g of an orange crude product were purified by columnchromatography (column with a diameter of 6.5 cm) on 180 g of silica gelwith 1:1 toluene/petroleum ether. This gave 3.8 g of pure titlecompound. R_(f) (toluene)=0.72.

The compounds of examples 13 and 14 were prepared in an analogousmanner.

Example 13 Preparation ofoctachloro-N,N′-bis(1H,1H-perfluorooctyl)perylene-3,4:9,10-tetracarboximide

Example 14 Preparation ofoctafluoro-N,N′-bis(1H,1H-perfluorooctyl)perylene-3,4:9,10-tetracarboximide

General Method for Determining the Field-Effect TransistorCharacteristics 1. Production of Semiconductor Substrates by Means ofPhysical Vapor Deposition (PVD)

The substrates used were high-doping n-type (100 nm) silicon wafers(conductivity <0.004 Ω⁻¹ cm) with a thermally deposited oxide layer (300nm) as the gate dielectric (area-based capacitance C_(i)=10 nF/cm²). Thecoated substrates were cleaned by rinsing with acetone and isopropanol.The semiconductor compounds were applied by vapor deposition underreduced pressure at defined deposition temperatures between 25 and 150°C. (typically at 125° C.), and deposited on the substrate with adeposition rate in the range from 0.3 to 0.5 Å/s and a pressure of 10⁻⁶Torr in a vacuum coating apparatus (Angstrom Engineering Inc., Canada).To measure the charge mobilities of the resulting material, TFTs wereprovided in top-contact configuration. To this end, source and drainelectrodes of gold (typically of channel length 100 μm and length/widthratio about 20) were deposited through a shadowmask by means of gasphase deposition. The electrical properties of the TFTs were determinedby means of a Keithley 4200-SCS semiconductor parameter analyzer.

2. Surface Treatment a) OTS-V

After the cleaning of the SiO₂-coated wafers by rinsing with acetone andisopropanol, the surface can additionally be modified, for example, withn-octadecyltriethoxysilane (OTS, C₁₈H₃₇Si(OC₂H₅)₃). To this end, a fewdrops of OTS (Aldrich Chem. Co.) were placed onto the preheated surface(about 100° C.) in a vacuum desiccator. The desiccator was evacuated andthe substrates were kept under reduced pressure (25 mm Hg) for at least5 hours. Finally, the substrates were baked at 110° C. for 15 minutes,rinsed with isopropanol and dried in a nitrogen stream.

b) Unmodified Surface

The SiO₂/Si substrates were rinsed with toluene, acetone andisopropanol, and dried in a nitrogen stream. The cleaned wafers wereused without further surface modification.

3. Purification

The compounds are purified by three-zone gradient sublimation.

Example 15 Field-Effect Transistor Comprising the Compound from Example2

The compound was deposited at 125° C. The component was analyzed bothunder nitrogen and in an air atmosphere. The results are listed in table1.

TABLE 1 Surface treatment N₂ Air*⁾ with OTS-V mobility μ (cm²/Vs) 0.270.20 I_(on)/I_(off) 1.4 × 10⁵ 1.5 × 10⁷ V_(t) (V) 22.0 30.2 withoutsurface treatment mobility μ (cm²/Vs) 2.9 × 10⁻⁵ n.d. I_(on)/I_(off) 1.3× 10³ n.d. V_(t) (V) 16.2 n.d. *relative air humidity: about 42% n.d.not determined

Example 16 Field-Effect Transistor Comprising the Compound from Example6.b

The compound was deposited at 125° C. The component was analyzed bothunder nitrogen and in an air atmosphere. The results are listed in table2.

TABLE 2 Surface treatment N₂ Air*⁾ with OTS-V mobility μ (cm²/Vs) 0.0600.044 I_(on)/I_(off) 20.3 28.4 V_(t) (V) 1.2 × 10³ 1.8 × 10³ withoutsurface mobility μ (cm²/Vs)   2.0 × 10⁻⁵ n.d. treatment I_(on)/I_(off)7.2 × 10² n.d. V_(t) (V) 17.9 n.d. *⁾relative air humidity: about 42%n.d. not determined

Example 17 Field-Effect Transistor Comprising the Compound from Example3

The compound was deposited at 125° C. The component was analyzed bothunder nitrogen and in an air atmosphere. The results are listed in table3.

TABLE 3 Surface treatment N₂ Air*⁾ with OTS-V mobility μ (cm²/Vs) 1.1 ×10⁻⁵ 3.9 × 10⁻⁶ I_(on)/I_(off) 3.9 × 10²  1.4 × 10³  V_(t) (V) 26.6 34.9*⁾relative air humidity: about 42%

Embodiments

-   1. The use of compounds of the general formula (I)

-   -   in which    -   Y¹ is O or NR^(a) where R^(a) is hydrogen or an organyl radical,    -   Y² is O or NR^(b) where R^(b) is hydrogen or an organyl radical,    -   Z¹, Z², Z³ and Z⁴ are each O or S and    -   the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are each        chlorine and/or fluorine,    -   where 1 or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴        radicals may also be CN and/or 1 R¹¹, R¹², R¹³, R¹⁴, R²¹, R²²,        R²³ and R²⁴ radical may be hydrogen, and    -   where, in the case that Y¹ is NR^(a), one of the Z¹ and Z²        radicals may also be NR^(c), where the R^(a) and R^(c) radicals        together are a bridging X group having from 2 to 5 atoms between        the flanking bonds, and    -   where, in the case that Y² is NR^(b), one of the Z³ and Z⁴        radicals may also be NR^(d), where the R^(b) and R^(d) radicals        together are a bridging X group having from 2 to 5 atoms between        the flanking bonds,    -   as emitter materials, charge transport materials or exciton        transport materials.

-   2. The use according to embodiment 1, wherein the compounds of the    formula (I) are selected from compounds of the formula (I.A)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have one        of the definitions given in embodiment 1.

-   3. The use according to embodiment 1, wherein the compounds of the    formula (I) are selected from compounds of the formula (I.Ba)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have one        of the definitions given in embodiment 1, and R^(a) and R^(b)        are each independently hydrogen or unsubstituted or substituted        alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl,        cycloalkenyl, heterocycloalkyl, aryl or heteroaryl.

-   4. The use according to embodiment 1, wherein the compounds of the    formula (I) are selected from compounds of the formulae (I.Bb1) and    (I.Bb2)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have one        of the definitions given in embodiment 1, and X is a divalent        bridging group having from 2 to 5 atoms between the flanking        bonds.

-   5. The use according to any one of the preceding embodiments,    wherein none of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴    radicals is hydrogen.

-   6. The use according to embodiment 5, wherein the R¹¹, R¹², R¹³,    R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are all chlorine.

-   7. The use according to embodiment 5, wherein the R¹¹, R¹², R¹³,    R¹⁴, R²¹, R²², R²³ and R²⁴ radicals are all fluorine.

-   8. The use of compounds of the general formula (I) as defined in any    of the preceding embodiments as electron conductors in organic    field-effect transistors, organic solar cells and in organic    light-emitting diodes.

-   9. The use according to embodiment 8 as semiconductor material in    organic field-effect transistors.

-   10. The use of compounds of the general formula (I) as defined in    any of embodiments 1 to 7 as emitter material in organic    light-emitting diodes.

-   11. The use of compounds of the general formula (I) as defined in    any of embodiment 1 to 7 as active material in organic    photovoltaics, especially as exciton transport material in excitonic    solar cells.

-   12. The use of compounds of the general formula (I) as defined in    any of embodiment 1 to 7 as light absorbers or light emitters.

-   13. The use of a compound of the general formula (I) as defined in    any of embodiment 1 to 7 for optical labels, for invisible marking    of products, as fluorescent dyes, as fluorescent labels for    biomolecules and as pigments.

-   14. The use of a compound of the general formula (I) as defined in    any of embodiment 1 to 7 as a fluorescent dye in a display based on    fluorescence conversion; in a light-collecting plastics part which    is optionally combined with a solar cell; as a pigment dye in    electrophoretic displays; as a fluorescent dye in an application    based on chemoluminescence.

-   15. A process for preparing compounds of the formula (I)

-   -   where R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴, Y¹, Y², Z¹, Z², Z³        and Z⁴ each have one of the definitions given in any of        embodiments 1 to 7,    -   in which    -   a) a compound of the formula (II)

-   -   -   in which        -   R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ are each selected            from hydrogen, Cl and CN, and        -   Y¹, Y², Z¹, Z², Z³ and Z⁴ each have one of the definitions            given in any of embodiments 1 to 7,        -   where at least one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³,            R²⁴ radicals is hydrogen, from 0 to 7 of the R¹¹, R¹², R¹³,            R¹⁴, R²¹, R²², R²³, R²⁴ radicals are each Cl and from 0 to 2            of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ radicals are            each CN,        -   is subjected to a chlorination to obtain a compound of the            formula (I)        -   in which the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴            radicals are each chlorine, where 1 or 2 of the R¹¹, R¹²,            R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals may also be CN, and            one of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴            radicals may be hydrogen,        -   and

    -   b) optionally, the compound of the formula (I) obtained in        step a) is subjected to a partial or full exchange of chlorine        for fluorine.

-   16. The process according to embodiment 15, wherein the chlorination    of the compound of the formula (II) is brought about by reaction    with chlorine in chlorosulfonic acid and in the presence of    catalytic amounts of iodine.

-   17. The process according to either of embodiment 15 and 16, wherein    the exchange of chlorine for fluorine on the compound of the    formula (I) obtained in step a) is brought about by reaction with an    alkali metal fluoride under essentially anhydrous conditions.

-   18. A compound of the general formula (I)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴, Y¹, Y¹, Z¹, Z²,        Z³ and Z⁴ each have one of the definitions given in embodiments        1 to 7, excluding N,N′-dimethylheptachloroperylimide and        N,N′-dimethyloctachloroperylimide.

-   19. A compound of the formula (I.A)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ each have one        of the definitions given in embodiment 1.

-   20. A compound of the formula (I.Ba)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴, R^(a) and R^(b)        each have one of the definitions given in embodiment 1.

-   21. A compound of the formula (I.Bb1) or (I.Bb2)

-   -   in which R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, R²⁴ and X each have        one of the definitions given in embodiment 1.

-   22. A compound according to any of embodiment 18 to 21, in which    R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ are each fluorine, where 1    or 2 of the R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴ radicals may    also be CN and/or 1 R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³ and R²⁴    radical may be hydrogen.

-   23. An organic field-effect transistor comprising a substrate having    at least one gate structure, a source electrode and a drain    electrode, and at least one compound of the formula (I) as defined    in any of embodiment 1 to 7 as an n-semiconductor.

-   24. An organic solar cell comprising at least one compound of the    formula (I) as defined in any of embodiment 1 to 7.

-   25. An OLED comprising at least one compound of the formula (I) as    defined in any of embodiment 1 to 7.

-   26. A substrate having a multitude of organic field-effect    transistors, wherein at least some of the field-effect transistors    comprise at least one compound of the formula (I) as defined in any    of embodiment 1 to 7 as an n-semiconductor.

-   27. A semiconductor component comprising at least one substrate as    defined in embodiment 26.

1. (canceled)
 2. A method of transporting a charge, the methodcomprising: conducting an electron through a material comprising acompound of formula (I.Ba):

wherein R^(a) represents hydrogen; an unsubstituted or substitutedcycloalkyl group; an unsubstituted or substituted aryl group; a2,2,3,3,3-pentafluoropropyl group; a 2,2-difluoroethyl group; a2,2,3,3,4,4,4-heptafluorobutyl group; a 2,2,3,3,3-pentafluoropropylgroup; a 1H,1H-pentadecafluorooctyl group; a 3-bromo-3,3-difluoropropylgroup; a 3,3,3-trifluoropropyl group; a 1H,1H,2H,2H-perfluorodecylgroup; a 3-(perfluorooctyl)propyl group; a 4,4-difluorobutyl group; a4,4,4-trifluorobutyl group; a 5,5,6,6,6-pentafluorohexyl group; a2,2-difluoropropyl group; a 2,2,2-trifluoroethyl group, or a2-bromo-2,2-difluoroethyl group; R^(b) represents hydrogen; anunsubstituted or substituted cycloalkyl group; an unsubstituted orsubstituted aryl group; a 2,2,3,3,3-pentafluoropropyl group; a2,2-difluoroethyl group; a 2,2,3,3,4,4,4-heptafluorobutyl group; a2,2,3,3,3-pentafluoropropyl group; a 1H,1H-pentadecafluorooctyl group; a3-bromo-3,3-difluoropropyl group; a 3,3,3-trifluoropropyl group; a1H,1H,2H,2H-perfluorodecyl group; a 3-(perfluorooctyl)propyl group; a4,4-difluorobutyl group; a 4,4,4-trifluorobutyl group; a5,5,6,6,6-pentafluorohexyl group; a 2,2-difluoropropyl group; a2,2,2-trifluoroethyl group, or a 2-bromo-2,2-difluoroethyl group; andeach of R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, and R²⁴, individually,represents chlorine or fluorine.
 3. The method according to claim 2,wherein each of R¹¹, R¹², R¹³, R¹⁴, R²¹, R²², R²³, and R²⁴ representschlorine.
 4. The method according to claim 2, wherein each of R¹¹, R¹²,R¹³, R¹⁴, R²¹, R²², R²³, and R²⁴ represents fluorine.
 5. The methodaccording to claim 2, wherein each of R^(a) and R^(b) representshydrogen.
 6. The method according to claim 2, wherein R^(a) representsan unsubstituted or substituted cycloalkyl group.
 7. The methodaccording to claim 2, wherein R^(a) represents an unsubstituted orsubstituted aryl group.
 8. The method according to claim 2, whereinR^(a) and R^(b) represent the same group.
 9. The method according toclaim 2, wherein each of R^(a) and R^(b) represents an unsubstituted orsubstituted aryl group.
 10. The method according to claim 2, wherein thecompound of formula (I.Ba) is selected from the group consisting of


11. The method according to claim 2, wherein each of R^(a) and R^(b)represents a 2,2,3,3,3-pentafluoropropyl group; a 2,2-difluoroethylgroup; a 2,2,3,3,4,4,4-heptafluorobutyl group; a2,2,3,3,3-pentafluoropropyl group; a 1H,1H-pentadecafluorooctyl group; a3-bromo-3,3-difluoropropyl group; a 3,3,3-trifluoropropyl group; a1H,1H,2H,2H-perfluorodecyl group; a 3-(perfluorooctyl)propyl group; a4,4-difluorobutyl; a 4,4,4-trifluorobutyl group; a5,5,6,6,6-pentafluorohexyl group; a 2,2-difluoropropyl group; a2,2,2-trifluoroethyl group; or a 2-bromo-2,2-difluoroethyl group.